Use of quinoline derivatives for the protection of cultivated plants from herbicides

ABSTRACT

In the method of protecting cultivated plants from the harmful effects of agrochemicals, quinoline derivatives of the formula ##STR1## in which R 1 , R 2  and R 3  independently of one another are hydrogen, halogen, nitro, cyano, alkyl or alkoxy, R 4 , R 5  and R 6  independently of one another are hydrogen, halogen or alkyl, X is an aliphatic, acyclic, saturated hydrocarbon radical having 1 to 3 carbon atoms and Y is a carboxyl group, or a salt thereof, a mercaptocarbonyl group or a salt thereof, a carboxylic acid ester group, a carboxylic acid thiolester group, an unsubstituted or substituted carboxylic acid amide group, a cyclized, unsubstituted or substituted derivative of a carboxylic acid amide group or a carboxylic acid hydrazide group, or X and Y together are an unsubstituted or substituted tetrahydrofuran-2-one ring, including acid addition salts and metal complexes thereof, or compositions containing such derivatives, are used. Novel quinoline derivatives and their preparation are also described.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of application Ser. No. 663,739 filed on Oct. 22,1984, abandoned, which is a continuation-in-part of application Ser. No.539,604, filed Oct. 6, 1983, abandoned, which in turn is acontinuation-in-part of application Ser. No. 490,912, filed May 2, 1983,abandoned.

The present invention relates to the use of quinoline derivatives forprotecting cultivated plants from the harmful effect of agrochemicals,compositions containing these quinoline derivatives, novel quinolinederivatives and the preparation of the quinoline derivatives. Thequinoline derivatives can also be used for regulating plant growth.

When agrochemicals, such as plant protection agents and especiallyherbicides, are used, the cultivated plants may be damaged to a certaindegree, depending on factors such as, for example, the dose ofagrochemicals and their method of application, the species of cultivatedplant, the nature of the soil and climatic conditions, for examplelength of time of exposure to light, temperature and amounts ofprecipitation. Thus, for example, it is known that cultivated plantswhich are to be protected from the adverse effect of undesirable plantgrowth may be damaged to a certain degree when an effective dose ofherbicides from very different classes of substances, such as triazines,urea derivatives, carbamates, thiolcarbamates, halogenoacetanilides,halogenophenoxyacetic acids and other classes, are used. Varioussubstances which are capable of specifically antagonising the harmfuleffect of a herbicide on the cultivated plants, i.e. of protecting thecultivated plants without at the same time noticeably influencing theherbicidal action on weeds to be combated, have already been proposed tosolve this problem. However, it has been found that the antidotesproposed frequently have only a narrow field of use, i.e. a particularantidote is frequently suitable only for use with individual species ofcultivated plants and/or for protecting the cultivated plants fromindividual herbicidal substances or classes of substances.

Thus, British Patent Specification 1,277,557 describes the treatment ofseeds or shoots of wheat and sorghum with certain oxamic acid esters andamides for protection from attack by "ALACHLOR"(N-methoxymethyl-N-chloroacetyl-2,6-diethylaniline). GermanOffenlegungsschriften 1,952,910 and 2,245,471 and French PatentSpecification 2,021,611 propose antidotes for treating cereal, maize andrice seeds to protect them from the harmful effect of herbicidallyactive thiolcarbamates. According to German Patent Specification1,567,075 and U.S. Pat. No. 3,131,509, hydroxyaminoacetanilides andhydantoins are used for protecting cereal seeds from carbamates.

Direct pre- or post-emergent treatment of certain useful plants withantidotes, as antagonists of certain classes of herbicides, on acultivated area is described in German Offenlegungsschriften 2,141,586and 2,218,097 and in U.S. Pat. No. 3,867,444.

Furthermore, according to German Offenlegungsschrift 2,402,983, maizeplants can be effectively protected from damage by chloroacetanilides bysupplying the soil with an N-disubstituted dichloroacetamide as anantidote.

According to European Patent Application 11,047, alkoximinobenzylcyanides in which the alkoxy group is substituted, inter alia, by anacetalised carbonyl group can also be used as agents for protectingcultivated plants from the harmful effect of herbicides of variousclasses of substances.

It has now been found that, surprisingly, a group of quinolinederivatives is outstandingly suitable for protecting cultivated plantsfrom the harmful effects of agrochemicals, for example plant protectionagents, especially herbicides. In the text which follows, thesequinoline derivatives are therefore also called "antidotes" or"safeners". They also have a plant growth-regulating action and areparticularly suitable for regulating the growth of dicotyledons,especially for increasing the yield of cultivated plants, especiallysoybean. Root growth and germination may also be promoted.

Quinoline derivtives which are suitable for protecting cultivated plantsfrom the harmful effects of agrochemicals are those of the formula I##STR2## in which R₁, R₂ and R₃ are independently of one another arehydrogen, halogen, nitro, cyano, alkyl or alkoxy, R₄, R₅ and R₆independently of one another are hydrogen, halogen or alkyl, X is analiphatic, acyclic, saturated hydrocarbon radical having 1 to 3 carbonatoms and Y is a carboxyl group or a salt thereof, a mercaptocarbonylgroup or a salt thereof, a carboxylic acid ester group, a carboxylicacid thiolester group, an unsubstituted or substituted carboxylic acidamide group, a cyclised, unsubstituted or substituted derivative of acarboxylic acid amide group or a carboxylic acid hydrazide group, or Xand Y together are an unsubstituted or substituted tetrahydrofuran-2-onering, including acid addition salts and metal complexes thereof.

The compounds of the formula I in which X is --CH(CH₃)--, --CH(C₂ H₅)--or --CH(A)--CH(E)--, A and E being as defined for formula I, or X and Ytogether are a tetrahydrofuran-2-one ring, they exist in the form ofoptical isomers. In the context of the present invention, thecorresponding compounds of the formula I are to be understood as meaningboth the optically pure isomers and the isomeric mixtures. Halogen is tobe understood as meaning fluorine, chlorine, bromine or iodine,especially chlorine, bromine or iodine.

An alkyl or alkoxy group R₁, R₂, R₃, R₄, R₅ or R₆ can be straight-chainor branched, and advantageously contains 1 to 18, in particular 1 to 6and preferably 1 to 3, carbon atoms.

An aliphatic, acyclic, saturated hydrocarbon radical X with 1 to 3carbon atoms is, in particular, one of the following groups: --CH₂ --,--CH₂ --CH₂ --, --CH(CH₃)--, --CH₂ --CH₂ --CH₂ --, --CH(C₂ H₅)--,--C(CH₃)₂ -- or --CH(A)--CH(E)--, in which one of the symbols A and E ishydrogen and the other is a methyl group.

A carboxylic acid ester group or carboxylic acid thiolester group Y is acorresponding acid radical which is esterified, for example, by asubstituted or unsubstituted aliphatic radical, or by a substituted orunsubstituted cycloaliphatic, aromatic or heterocyclic radical, whichmay be bonded via an aliphatic radical.

The preferred carboxylic acid ester radical is the radical --COOR₇ andthe preferred carboxylic acid thiolester radical is the radical --COSR₈,in which R₇ and R₈ are as defined as follows: a substituted orunsubstituted alkyl, alkenyl, alkinyl, cycloalkyl, phenyl or naphthylradical or a substituted or unsubstituted heterocyclic radical. Theradicals --COOR₇ and --COSR₈ also include the free acids, in which R₇and R₈ are hydrogen, and the salts thereof, in which R₇ and R₈ arecations. Particularly suitable salt-forming agents here are metals andorganic nitrogen bases, especially quaternary ammonium bases. Metalswhich are suitable for salt formation are alkaline earth metals, such asmagnesium or calcium, but especially alkali metals, such as lithium and,in particular, potassium and sodium. Transition metals, for exampleiron, nickel, cobalt, copper, zinc, chromium or manganese, are alsosuitable salt-forming agents. Examples of nitrogen bases which aresuitable for salt formation are primary, secondary and tertiaryaliphatic and aromatic amines, which may be hydroxylated on thehydrocarbon radical, such as methylamine, ethylamine, propylamine,isopropylamine, the four isomeric butylamines, dimethylamine,diethylamine, dipropylamine, diisopropylamine, di-n-butylamine,pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine,tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline, andmethanolamine, ethanolamine, propanolamine, dimethanolamine,diethanolamine and triethanolamine. Organic nitrogen bases also includequaternary ammonium bases. Examples of quaternary ammonium bases aretetraalkylammonium cations in which the alkyl radicals independently ofone another are straight-chain or branched C₁ -C₆ -alkyl groups, such asthe tetramethylammonium cation, the tetraethylammonium cation or thetrimethylethylammonium cation, and also the trimethylbenzylammoniumcation, the triethylbenzylammonium cation and thetrimethyl-2-hydroxyethylammonium cation. Particularly preferredsalt-forming agents are the ammonium cation and trialkylammonium cationsin which the alkyl radicals independently of one another arestraight-chain or branched, unsubstituted or hydroxy-substituted C₁ -C₆-alkyl groups, in particular C₁ -C₂ -alkyl groups, for example thetrimethylammonium cation, the triethylammonium cation and thetri-(2-hydroxyethylene)-ammonium cation.

A carboxylic acid amide group Y is a corresponding amide radical, whichcan be unsubstituted or mono-or disubstituted on the nitrogen atom or inwhich the nitrogen atom is a constituent of a substituted orunsubstituted heterocyclic radical. Examples of substituents on theamide group are substituted or unsubstituted aliphatic radicals, whichmay be bonded via an oxygen atom, substituted or unsubstitutedcycloaliphatic, aromatic or heterocyclic radicals, which may be bondedvia an aliphatic radical, and unsubstituted or mono- or di-substitutedamino groups.

The preferred carboxylic acid amide radical is the radical --CONR₉ R₁₀,in which R₉ is hydrogen, a substituted or unsubstituted alkyl, alkenyl,alkinyl, cycloalkyl, phenyl or naphthyl radical, a substituted orunsubstituted heterocyclic radical or an alkoxy radical and R₁₀ ishydrogen, amino, mono- or di-substituted amino or a substituted orunsubstituted alkyl, alkenyl, cycloalkyl or phenyl radical, or R₉ andR₁₀, together with the nitrogen atom to which they are bonded, are asubstituted or unsubstituted heterocyclic radical.

Examples of substituents on the organic radicals R₇, R₈, R₈, R₉ and R₁₀are halogen, nitro, cyano, hydroxyl, alkyl, halogenoalkyl, alkoxy, whichcan be interrupted by one or more oxygen atoms, alkylthio,halogenoalkoxy, hydroxyalkoxy, which can be interrupted by one or moreoxygen atoms, hydroxyalkylthio, alkoxycarbonyl, amino, alkylamino,dialkylamino, hydroxyalkylamino, di-(hydroxyalkyl)-amino,aminoalkylamino, cycloalkyl, substituted or unsubstituted phenyl,substituted or unsubstituted phenoxy and substituted or unsubstitutedheterocyclic radicals.

Heterocyclic radicals are to be understood as preferably meaning 5- to6-membered, saturated or unsaturated, substituted or unsubstitutedmonocyclic heterocyclic radicals having 1 to 3 hetero-atoms from thegroup comprising N, O and S, for example furan, tetrahydrofuran,tetrahydropyran, tetrahydropyrimidine, pyridine, piperidine, morpholineand imidazole.

Cycloalkyl radicals are to be understood particularly as meaning thosehaving 3 to 8 carbon atoms, especially 3 to 6 carbon atoms.

Aliphatic acyclic radicals in the substituent Y can be straight-chain orbranched and advantageously have not more than 18 carbon atoms. A lowernumber of carbon atoms is frequently advantageous, especially incomposite substituents.

A cyclised derivative Y of a carboxylic acid amide group is, inparticular, a substituted or unsubstituted oxazolin-2-yl radical,preferably an unsubstituted oxazolin-2-yl radical.

X and Y can together be a substituted or unsubstitutedtetrahydrofuran-2-one ring, preferably an unsubstitutedtetrahydrofuran-2-one ring, especially an unsubstitutedtetrahydrofuran-2-on-3-yl ring.

Examples of salt-forming agents are organic and inorganic acids.Examples of organic acids are acetic acid, trichloroacetic acid, oxalicacid, benzenesulfonic acid and methanesulfonic acid. Examples ofinorganic acids are hydrochloric acid, hydrobromic acid, hydriodic acid,sulfuric acid, phosphoric acid, phosphorous acid and nitric acid.

Examples of suitable metal complexing agents are elements of main groups3 and 4, such as aluminium, tin and lead, and of sub-groups 1 to 8, forexample chromium, manganese, iron, cobalt, nickel, zirconium, zinc,copper, silver and mercury. Sub-group elements of the 4th period arepreferred.

Compounds of the formula I which belong to the groups of compoundslisted below are particularly suitable for the use according to theinvention.

(a) Compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and X areas defined for formula I and Y is a substituted or unsubstitutedoxazolin-2-yl radical, --COOR₇, --COSR₈ or --CONR₉ R₁₀, in which R₇, R₈and R₉ are hydrogen, substituted or unsubstituted alkyl, alkenyl,alkinyl, cycloalkyl, phenyl or naphthyl radicals or substituted orunsubstituted heterocyclic radicals, or R₇ and R₈ are cations, or R₉ isan alkoxy radical, and in which R₁₀ is hydrogen, amino, mono- ordi-substituted amino or a substituted or unsubstituted alkyl, alkeny,cycloalkyl or phenyl radical, or R₉ and R₁₀, together with the nitrogenatom to which they are bonded, are a substituted or unsubstitutedheterocyclic radical, or X and Y together are a substituted orunsubstituted tetrahydrofuran-2-one ring, including acid addition saltsand metal complexes thereof; preferred compounds of group (a) are, assub-group a/1, those in which R₁, R₂ , R₃, R₄, R₅, R₆ and X are asdefined for formula I and Y is a substituted or unsubstitutedoxazolin-2-yl radical, --COOR₇, --COSR₈ or --CONR₉ R₁₀, in which R₇ andR₈ independently of one another are hydrogen or cations; alkyl, which isunsubstituted or substituted by halogen, nitro, cyano, hydroxyl, alkoxy,which can be interrupted by one or more oxygen atoms, alkylthio,halogenoalkoxy, hydroxyalkoxy, which can be interrupted by one or moreoxygen atoms, hydroxyalkylthio, alkoxycarbonyl, dialkylamino,cycloalkyl, substituted or unsubstituted phenyl, substituted orunsubstituted phenoxy or a substituted or unsubstituted heterocyclicradical; alkenyl, which is unsubstituted or substituted by halogen orsubstituted or unsubstituted phenyl; alkinyl, which is unsubstituted orsubstituted by halogen or hydroxyl; cycloalkyl, which is unsubstitutedor substituted by halogen, alkyl or alkoxy; phenyl, which isunsubstituted or substituted by halogen, nitro, cyano, alkyl, alkoxy,alkoxycarbonyl or halogenoalkyl; naphthyl, which is unsubstituted orsubstituted by halogen, nitro or alkyl; or substituted or unsubstitutedheterocyclic radicals; R₉ is hydrogen; alkyl, which is unsubstituted orsubstituted by halogen, cyano, hydroxyl, amino, alkylamino,dialkylamino, hydroxyalkylamino, di-(hydroxyalkyl)-amino,aminoalkylamino, alkoxy, alkoxycarbonyl, phenyl, which is unsubstitutedor substituted by halogen, nitro, alkyl or alkoxy, cycloalkyl or asubstituted or unsubstituted heterocyclic radical; alkoxy; alkenyl;cycloalkyl; phenyl, which is unsubstituted or substituted by halogen,nitro, cyano, alkyl, alkoxy or halogenoalkyl; naphthyl, which isunsubstituted or substituted by nitro or alkyl; or a substituted orunsubstituted heterocyclic radical; and R₁₀ is hydrogen; amino;dialkylamino; alkyl, which is unsubstituted or substituted by hydroxyl,cyano or alkoxy; alkenyl; cycloalkyl; or phenyl, or R₉ and R₁₀, togetherwith the nitrogen atom to which they are bonded, are a substituted orunsubstituted heterocyclic radical, or X and Y together are asubstituted or unsubstituted tetrahydrofuran-2-one ring, including acidaddition salt and metal complexes thereof; preferred sub-groups ofcompounds of group a/1 are those in which

(i) R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Y is--COOR₇, in which R₇ is hydrogen, an alkali metal cation or a quaternaryammonium cation; C₁ -C₁₈ -alkyl; C₁ -C₁₀ -alkyl, which is substituted byhalogen, nitro, cyano, hydroxyl, C₁ -C₈ -alkoxy, which can beinterrupted by one or more oxygen atoms, C₁ -C₄ -alkylthio, C₂ -C₆-halogenoalkoxy, C₂ -C₆ -hydroxyalkoxy, which can be interrupted by oneor more oxygen atoms, C₂ -C₆ -hydroxyalkylthio, C₁ -C₄ -alkoxycarbonyl,C₂ -C₁₂ -dialkylamino or substituted or unsubstituted phenoxy; C₁ -C₆-alkyl, which is substituted by phenyl, which is unsubstituted orsubstituted by halogen, nitro, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy, C₃ -C₆-cycloalkyl or a substituted or unsubstituted, saturated or unsaturatedheterocyclic radical having 1 to 3 hetero-atoms; C₃ -C₁₀ -alkenyl, whichis unsubstituted or substituted by halogen or substituted orunsubstituted phenyl; C₃ -C₆ -alkinyl, which is unsubstituted orsubstituted by halogen or hydroxyl; C₃ -C₈ -cycloalkyl, which isunsubstituted or substituted by halogen, C₁ -C₃ -alkyl or C₁ -C₃-alkoxy; phenyl, which is unsubstituted or substituted by halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl orC₁ -C₂ -halogenoalkyl; naphthyl, which is unsubstituted or substitutedby halogen, nitro or C₁ -C₃ -alkyl; or a 5- or 6-membered, saturated orunsaturated, substituted or unsubstituted heterocyclic ring having 1 to3 hetero-atoms from the group comprising N, O and S, and, of thesecompounds, especially those in which R₁, R₂, R₃, R₄, R₅, R₆ and X are asdefined for formula I and Y is --COOR₇, in which R₇ is hydrogen, analkali metal cation or a quaternary ammonium cation chosen from thegroup comprising the ammonium cation and the trimethyl-, triethyl- andtri-(2-hydroxyethylene)-ammonium cations; C₁ -C₁₈ -alkyl; C₁ -C₁₀-alkyl, which is substituted by 1 or 2 hydroxyl groups; C₁ -C₄ -alkyl,which is substituted by 1 to 3 chlorine or bromine atoms, a nitro group,a cyano group, a C₁ -C₄ -alkoxy group, a C₂ -C₈ -alkoxy group, which isinterrupted by 1 or 2 oxygen atoms, a hydroxy-C₁ -C₄ -alkoxy group, ahydroxy-C₂ -C₆ -alkoxy group, which is interrupted by 1 or 2 oxygenatoms, a C₁ -C₄ -alkoxycarbonyl group, a di-(C₁ -C₄ -alkyl)-amino group,a phenyl radical, which is unsubstituted or substituted by chlorine ormethoxy, a cyclohexyl radical or a furan, tetrahydrofuran,tetrahydropyran, pyridino, piperidino or morpholino radical; C₃ -C₁₀-alkenyl; C₂ -C₄ -alkinyl, which is unsubstituted or substituted by ahydroxyl group; cyclohexyl, which is unsubstituted or substituted by 1or 2 methyl groups, phenyl, which is unsubstituted or substituted by 1or 2 substituents from the group comprising chlorine, nitro, C₁ -C₄-alkyl and methoxy; naphthyl; or pyridine;

(ii) R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Y is--COSR₈, in which R₈ is hydrogen; C₁ -C₁₈ -alkyl; C₁ -C₁₀ -alkyl, whichis substituted by halogen, nitro, cyano, hydroxyl, C₁ -C₈ -alkoxy, whichcan be interrupted by one or more oxygen atoms, C₁ -C₄ -alkylthio, C₂-C₆ -halogenoalkoxy, C₂ -C₆ -hydroxyalkoxy, which can be interrupted byone or more oxygen atoms, C₂ -C₆ -hydroxyalkylthio, C₁ -C₄-alkoxycarbonyl, C₂ -C₁₂ -dialkylamino or substituted or unsubstitutedphenoxy; C₁ -C₆ -alkyl, which is substituted by phenyl, which isunsubstituted or substituted by halogen, nitro, C₁ -C₃ -alkyl or C₁ -C₃-alkoxy, C₃ -C₆ -cycloalkyl or a substituted or unsubstituted, saturatedor unsaturated heterocyclic radical having 1 to 3 hetero-atoms; C₃ -C₁₀-alkenyl, which is unsubstituted or substituted by halogen orsubstituted or unsubstituted phenyl; C₃ -C₆ -alkinyl, which isunsubstituted or substituted by halogen or hydroxyl; C₃ -C₈ -cycloalkyl,which is unsubstituted or substituted by halogen, C₁ -C₃ -alkyl or C₁-C₃ -alkoxy; phenyl, which is unsubstituted or substituted by halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl orC₁ -C₂ -halogenoalkyl; naphthyl, which is unsubstituted or substitutedby halogen, nitro or C₁ -C₃ -alkyl; or a 5- or 6-membered, saturated orunsaturated, substituted or unsubstituted heterocyclic ring having 1 to3 hetero-atoms from the group comprising N, O and S, and, of thesecompounds, especially those in which R₁, R₂, R₃, R₄, R₅, R₆ and X are asdefined for formula I and Y is --COSR₈, in which R₈ is C₁ -C₁₂ -alkyl;C₁ -C₄ -alkyl, which is substituted by a C₁ -C₄ -alkoxycarbonyl group;or phenyl, which is unsubstituted or substituted by a chlorine atom;

(iii) R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Y is--CONR₉ R₁₀, in which R₉ is hydrogen; C₁ -C₁₈ alkyl, C₂ -C₈ -alkyl,which is substituted by amino; C₂ -C₆ -alkyl, which is substituted byhalogen, hydroxyl, C₁ -C₆ -alkylamino, C₂ -C₈ -dialkylamino, C₂ -C₆-hydroxyalkylamino, C₂ -C₆ -di-(hydroxyalkyl)-amino, C₂ -C₆-aminoalkylamino or C₁ -C₄ -alkoxycarbonyl; C₁ -C₄ -alkyl, which issubstituted by cyano, C₁ -C₄ -alkoxy, phenyl, which is unsubstituted orsubstituted by halogen, nitro, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy, C₃ -C₆-cycloalkyl or a 5- or 6-membered, saturated or unsaturated, substitutedor unsubstituted heterocyclic ring having 1 to 3 hetero-atoms from thegroup comprising N, O and S; C₁ -C₃ -alkoxy; C₃ -C₆ -alkenyl; C₃ -C₈-cycloalkyl; phenyl, which is unsubstituted or substituted by halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₂ -halogenoalkyl; ornaphthyl, which is unsubstituted or substituted by nitro or methyl; andR₁₀ is hydrogen; amino; C₂ -C₄ -dialkylamino; C₁ -C₆ -alkyl; C₁ -C₄-alkyl, which is substituted by hydroxyl or cyano; C₂ -C₆ -alkoxyalkyl;C₃ -C₆ -alkenyl; C₃ -C₆ -cycloalkyl; or phenyl; or in which R₉ and R₁₀,together with the nitrogen atom to which they are bonded, are a 5- or6-membered, saturated or unsaturated, substituted or unsubstitutedheterocyclic ring, which can also contain 1 or 2 other hetero-atoms fromthe group comprising N, O and S, and of these compounds especially thosein which R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Yis --CONR₉ R₁₀, in which R₉ is hydrogen; C₁ -C₁₈ -alkyl; C₂ -C₈ -alkyl,which is substituted by an amino group; C₂ -C₆ -alkyl, which issubstituted by a hydroxyl group; C₂ -C₄ -alkyl, which is substituted bya chlorine or bromine atom, a C₁ -C₄ -alkylamino group, a di-(C₁ -C₄-alkyl)-amino group, a C₁ -C₄ -hydroxyalkylamino group, a di-(C₁ -C₃-hydroxyalkyl)-amino group, a C₁ -C₄ -alkoxy group or a C₁ -C₄-alkoxycarbonyl group; C₁ -C₄ -alkyl, which is substituted by a cyanogroup, a phenyl radical, which is unsubstituted or substituted bychlorine, or a furanyl, tetrahydrofuranyl, piperidino or morpholinoradical; C₁ -C₃ -alkoxy; C₂ -C₄ -alkenyl; cyclohexyl, which isunsubstituted or substituted by a methyl group; or phenyl, which isunsubstituted or substituted by 1 or 2 substituents from the groupcomprising chlorine, nitro, cyano, methyl, ethyl, methoxy andtrifluoromethyl, and R₁₀ is hydrogen; C₁ -C₆ -alkyl; C₁ -C₄ -alkyl,which is substituted by a hydroxyl group or a cyano group; C₂ -C₄-alkoxyalkyl; C₂ -C₄ -alkenyl; cyclohexyl; or phenyl, or R₉ and R₁₀,together with the nitrogen atom to which they are bonded, are apiperidino, tetrahydropyrimidino, morpholino or imidazolyl radical whichis unsubstituted or substituted by 1 or 2 methyl groups;

(iv) R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Y isa substituted or unsubstituted oxazolin-2-yl radical, and of thesecompounds, especially those in which R₁, R₂, R₃, R₄, R₅, R₆ and X are asdefined for formula I and Y is an unsubstituted oxazolin-2-yl radical;and

(v) R₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I and X and Ytogether are a substituted or unsubstituted tetrahydrofuran-2-one ring,and of these compounds, especially those in which R₁, R₂, R₃, R₄, R₅ andR₆ are as defined for formula I and X and Y together are anunsubstituted tetrahydrofuran-2-one ring, in particular an unsubstitutedtetrahydrofuran-2-on-3-yl ring;

(b) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --CH₂ --;

(c) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --CH₂ --CH₂ ;

(d) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --CH(CH₃)--;

(e) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --CH(A)--CH(E)--, in which one of thesymbols A and E is hydrogen and the other is a methyl group;

(f) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --CH₂ --CH₂ --CH₂ --;

(g) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --CH(C₂ H₅)--;

(h) compounds of the formula I in which R₁, R₂, R₃, R₄, R₅, R₆ and Y areas defined for formula I and X is --C(CH₃)₂ --;

(i) compounds of the formula I in which R₁, R₂ and R₃ independently ofone another are hydrogen, halogen, nitro or C₁ -C₃ -alkyl, R₄, R₅ and R₆independently of one another are hydrogen or C₁ -C₃ -alkyl and X and Yare as defined for formula I;

(k) compounds of the formula I in which R₁ is hydrogen or halogen, R₂ ishydrogen, R₃ is hydrogen, halogen, nitro or C₁ -C₃ -alkyl, R₄ ishydrogen, R₅ is hydrogen, R₆ is hydrogen or C₁ -C₃ -alkyl and X and Yare as defined for formula I;

(l) compounds of the formula I in which R₁ is hydrogen, chlorine, iodineor bromine, R₂ is hydrogen, R₃ is hydrogen, chlorine, iodine, bromine,nitro, methyl or ethyl, R₄ is hydrogen, R₅ is hydrogen, R₆ is hydrogenor methyl and X and Y are as defined for formula I;

(m) compounds of the formula I in which R₁, R₂ and R₃ independently ofone another are hydrogen, halogen, nitro or C₁ -C₃ -alkyl, R₄, R₅ and R₆independently of one another are hydrogen of C₁ -C₃ -alkyl, X is asdefined for formula I and Y is a substituted or unsubstitutedoxazolin-2-yl radical, --COOR₇, --COSR₈ or --CONR₉ R₁₀, in which R₇ ishydrogen, an alkali metal cation or a quaternary ammonium cation; C₁-C₁₈ -alkyl; C₁ -C₁₀ -alkyl, which is substituted by halogen, nitro,cyano, hydroxyl, C₁ -C₈ -alkoxy, which can be interrupted by one or moreoxygen atoms, C₁ -C₄ -alkylthio, C₂ -C₆ -halogenoalkoxy, C₂ -C₆-hydroxyalkoxy, which can be interrupted by one or more oxygen atoms, C₂-C₆ -hydroxyalkylthio, C₁ -C₄ -alkoxycarbonyl, C₂ -C₁₂ -dialkylamino orsubstituted or unsubstituted phenoxy; C₁ -C₆ -alkyl, which issubstituted by phenyl, which is unsubstituted or substituted by halogen,nitro, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy, C₃ -C₆ -cycloalkyl or asubstituted or unsubstituted, saturated or unsaturated heterocyclicradical having 1 to 3 hetero-atoms; C₃ -C₁₀ -alkenyl, which isunsubstituted or substituted by halogen or substituted or unsubstitutedphenyl; C₃ -C₆ -alkinyl, which is unsubstituted or substituted byhalogen or hydroxyl; C₃ -C₈ -cycloalkyl, which is unsubstituted orsubstituted by halogen, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy; phenyl, whichis unsubstituted or substituted by halogen, nitro, cyano, C₁ -C₄ -alkyl,C₁ -C₄ alkoxy, C₁ -C₄ -alkoxycarbonyl or C₁ -C₂ -halogenoalkyl;naphthyl, which is unsubstituted or substituted by halogen, nitro or C₁-C₃ -alkyl; or a 5- or 6-membered, saturated or unsaturated, substitutedor unsubstituted heterocyclic ring having 1 to 3 hetero-atoms from thegroup comprising N, O and S, R₈ is hydrogen; C₁ -C₁₈ -alkyl; C₁ -C₁₀-alkyl, which is substituted by halogen, nitro, cyano, hydroxyl, C₁ -C₈-alkoxy, which can be interrupted by one or more oxygen atoms, C₁ -C₄-alkylthio, C₂ -C₆ -halogenoalkoxy, C₂ -C₆ -hydroxyalkoxy, which can beinterrupted by one or more oxygen atoms, C₂ -C₆ -hydroxyalkylthio, C₁-C₄ -alkoxycarbonyl, C₂ -C₁₂ -dialkylamino or substituted orunsubstituted phenoxy; C₁ -C₆ -alkyl, which is substituted by phenyl,which is unsubstituted or substituted by halogen, nitro, C₁ -C₃ -alkylor C₁ -C₃ -alkoxy, C₃ -C₆ -cycloalkyl or a substituted or unsubstituted,saturated or unsaturated heterocyclic radical having 1 to 3hetero-atoms; C₃ -C₁₀ -alkenyl, which is unsubstituted or substituted byhalogen or substituted or unsubstituted phenyl; C₃ -C₆ -alkinyl, whichis unsubstituted or substituted by halogen or hydroxyl; C₃ -C₈-cycloalkyl, which is unsubstituted or substituted by halogen, C₁ -C₃-alkyl or C₁ -C₃ -alkoxy; phenyl, which is unsubstituted or substitutedby halogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkoxycarbonyl or C₁ -C₂ -halogenoalkyl; naphthyl, which isunsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl; or a 5-or 6-membered, saturated or unsaturated, substituted or unsubstitutedheterocyclic ring having 1 to 3 hetero-atoms from the group comprisingN, O and S, in which R₉ is hydrogen; C₁ -C₁₈ alkyl; C₂ -C₈ -alkyl, whichis substituted by amino; C₂ -C₆ -alkyl, which is substituted by halogen,hydroxyl, C₁ -C₆ -alkylamino, C₂ -C₈ -dialkylamino, C₂ -C₆-hydroxyalkylamino, C₂ -C₆ -di-(hydroxyalkyl)-amino, C₂ -C₆-aminoalkylamino or C₁ -C₄ -alkoxycarbonyl; C₁ -C₄ -alkyl, which issubstituted by cyano, C₁ -C₄ -alkoxy, phenyl, which is unsubstituted orsubstituted by halogen, nitro, C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy, C₃ -C₆-cycloalkyl or a 5- or 6-membered, saturated or unsaturated, substitutedor unsubstituted heterocyclic ring having 1 to 3 hetero-atoms from thegroup comprising N, O and S; C₁ -C₃ -alkoxy; C₃ -C₆ -alkenyl; C₃ -C₈-cycloalkyl; phenyl, which is unsubstituted or substituted by halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₂ -halogenoalkyl; ornaphthyl, which is unsubstituted or substituted by nitro or methyl; andR₁₀ is hydrogen; amino; C₂ -C₄ -dialkylamino, C₁ -C₆ -alkyl; C₁ -C₄-alkyl, which is substituted by hydroxyl or cyano, C₂ -C₆ -alkoxyalkyl;C₃ -C₆ -alkenyl; C₃ -C₆ -cycloalkyl; or phenyl; or in which R₉ and R₁₀,together with the nitrogen atom to which they are bonded, are a 5- or6-membered, saturated or unsaturated, substituted or unsubstitutedheterocyclic ring, which can also contain 1 or 2 other hetero-atoms fromthe group comprising N, O and S, or X and Y together are a substitutedor unsubstituted tetrahydrofuran-2-one ring.

(n) compounds of the formula I in which R₁ is hydrogen, chlorine, iodineor bromine, R₂ is hydrogen, R₃ is hydrogen, chlorine, iodine, bromine,nitro, methyl or ethyl, R₄ is hydrogen, R₅ is hydrogen, R₆ is hydrogenor methyl, X is as defined for formula I and Y is an unsubstitutedoxazolin-2-yl radical, --COOR₇, --COSR₈ or --CONR₉ R₁₀, in which R₇ ishydrogen, an alkali metal cation or a quaternary ammonium cation chosenfrom the group comprising the ammonium cation and the trimethyl-,triethyl- and tri-(2-hydroxyethylene)-ammonium cations; C₁ -C₁₈ -alkyl;C₁ -C₁₀ -alkyl, which is substituted by 1 or 2 hydroxyl groups; C₁ -C₄-alkyl, which is substituted by 1 to 3 chlorine or bromine atoms, anitro group, a cyano group, a C₁ -C₄ -alkoxy group, a C₂ -C₈ -alkoxygroup, which is interrupted by 1 or 2 oxygen atoms, a hydroxy-C₁ -C₄-alkoxy group, a hydroxy-C₂ -C₆ -alkoxy group, which is interrupted by 1or 2 oxygen atoms, a C₁ -C₄ -alkoxycarbonyl group, a di-(C₁ -C₄-alkyl)amino group, a phenyl radical, which is unsubstituted orsubstituted by chlorine or methoxy, a cyclohexyl radical or a furan,tetrahydrofuran, tetrahydropyran, pyridino, piperidino or morpholinoradical; C₃ -C₁₀ -alkenyl; C₂ -C₄ -alkinyl, which is unsubstituted orsubstituted by a hydroxyl group; cyclohexyl, which is unsubstituted orsubstituted by 1 or 2 methyl groups; phenyl, which is unsubstituted orsubstituted by 1 or 2 substituents from the group comprising chlorine,nitro, C₁ -C₄ -alkyl and methoxy; naphthyl; or pyridine, R₈ is C₁ -C₁₂-alkyl; C₁ -C₄ -alkyl, which is substituted by a C₁ -C₄ -alkoxycarbonylgroup; or phenyl, which is unsubstituted or substituted by a chlorineatom; R₉ is hydrogen; C₁ -C₁₈ -alkyl; C₂ -C₈ -alkyl, which issubstituted by an amino group; C₂ -C₆ -alkyl, which is substituted by ahydroxyl group; C₂ -C₄ -alkyl, which is substituted by a chlorine orbromine atom, a C₁ -C₄ -alkylamino group, a di-(C₁ -C₄ -alkyl)-aminogroup, a C₁ -C₄ -hydroxyalkylamino group, a di-(C₁ -C₃-hydroxyalkyl)-amino group, a C₁ -C₄ -alkoxy group or a C₁ -C₄-alkoxycarbonyl group; C₁ -C₄ -alkyl, which is substituted by a cyanogroup, a phenyl radical, which is unsubstituted or substituted bychlorine, or a furanyl, tetrahydrofuranyl, piperidino or morpholinoradical; C₁ -C₃ -alkoxy; C₂ -C₄ -alkenyl; cyclohexyl, which isunsubstituted or substituted by a methyl group; or phenyl, which isunsubstituted or substituted by 1 or 2 substituents from the groupcomprising chlorine, nitro, cyano, methyl, ethyl, methoxy andtrifluoromethyl, and R₁₀ is hydrogen; C₁ -C₆ -alkyl; C₁ -C₄ -alkyl,which is substituted by a hydroxyl group or a cyano group; C₂ -C₄-alkoxyalkyl; C₂ -C₄ -alkenyl; cyclohexyl; or phenyl, or R₉ and R₁₀,together with the nitrogen atom to which they are bonded, are apiperidino, tetrahydropyrimidino, morpholino or imidazolyl radical whichis unsubstituted or substituted by 1 or 2 methyl groups, or X and Ytogether are an unsubstituted tetrahydrofuran-2-on-3-yl ring;

(o) compounds of the above group (m) in which X is --CH₂ --, with theproviso that if, at the same time, R₁ is hydrogen, chlorine, bromine oriodine, R₂ is hydrogen, nitro or methyl, R₃ is hydrogen, chlorine,bromine, nitro, methyl or ethyl, R₄ and R₅ are hydrogen, R₆ is hydrogenor methyl and Y is --COOR₇ or --CONR₉ R₁₀,

(i) R₇ is not hydrogen or C₁ -C₄ -alkyl which is unsubstituted orsubstituted by diethylamino, and

(ii) R₉ is not hydrogen, C₁ -C₄ -alkyl, allyl or phenyl which isunsubstituted or substituted by p-chloro, if R₁₀ is hydrogen, amino, C₁-C₄ -alkyl, allyl or phenyl, and

(iii) R₉ and R₁₀, together with the nitrogen atom to which they arebonded, are not a morpholine ring;

(p) compounds of the above group (n) in which X is --CH₂ --, with theproviso that if, at the same time, R₁ is hydrogen, chlorine, iodine orbromine, R₂ is hydrogen, R₃ is hydrogen, chlorine, bromine, nitro,methyl or ethyl, R₄ and R₅ are hydrogen, R₆ is hydrogen or methyl and Yis --COOR₇ or --CONR₉ R₁₀,

(i) R₇ is not hydrogen or C₁ -C₄ -alkyl which is unsubstituted orsubstituted by diethylamino, and

(ii) R₉ is not hydrogen, C₁ -C₄ -alkyl, allyl or phenyl which isunsubstituted or substituted by p-chloro, if R₁₀ is hydrogen, C₁ -C₄-alkyl, allyl or phenyl, and

(iii) R₉ and R₁₀, together with the nitrogen atom to which they arebonded, are not a morpholine ring;

(q) compounds of the above group (m), in which X is --CH₂ --CH₂ --, withthe proviso that if, at the same time, R₁, R₂, R₃, R₄, R₅ and R₆ arehydrogen and Y is --COOR₇, R₇ is not hydrogen;

(r) compounds of the above group (n) in which X is --CH₂ --CH₂ --, withthe proviso that if R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen and Y is--COOR₇, R₇ is not hydrogen;

(s) compounds of the above group (m) in which X is --CH(CH₃)--, with theproviso that if R₁ is hydrogen or chlorine, R₂ is hydrogen, R₃ ishydrogen or chlorine, R₄ and R₅ are hydrogen, R₆ is hydrogen or methyland Y is --COOR₇ or --CONR₉ R₁₀,

(i) R₇ is not ethoxy, and

(ii) R₉ is not hydrogen, ethyl, sec.-butyl or allyl, if R₁₀ is hydrogen,ethyl, sec.-butyl or allyl, and

(iii) R₉ and R₁₀, together with the nitrogen atom to which they arebonded, are not a pyrrolidino ring;

(t) compounds of the above group (n) in which X is --CH(CH₃)--, with theproviso that if, at the same time, R₁ is hydrogen or chlorine, R₂ ishydrogen, R₃ is hydrogen or chlorine, R₄ and R₅ are hydrogen, R₆ ishydrogen or methyl and Y is --COOR₇ or --CONR₉ R₁₀,

(i) R₇ is not ethyl and

(ii) R₉ is not hydrogen, ethyl, sec.-butyl or allyl, if R₁₀ is hydrogen,ethyl, sec.-butyl or allyl;

(u) compounds of the above group (m) in which X is --CH(A)--CH(E)--, inwhich one of the symbols A and E is hydrogen and the other is a methylgroup;

(v) compounds of the above group (n) in which X is --CH(A)--CH(E)--, inwhich one of the symbols A and E is hydrogen and the other is a methylgroup;

(w) compounds of the above group (m) in which X is --CH₂ --CH₂ --CH₂ --,with the proviso that if, at the same time, R₁, R₂, R₃, R₄, R₅ and R₆are hydrogen and Y is --COOR₇ or --CONR₉ R₁₀, R₇ is not hydrogen, methylor ethyl and R₉ and R₁₀ are not both ethyl;

(x) compounds of the above group (n) in which X is --CH₂ --CH₂ --CH₂ --,with the proviso that if, at the same time, R₁, R₂, R₃, R₄, R₅ and R₆are hydrogen and Y is --COOR₇ or --CONR₉ R₁₀, R₇ is not hydrogen, methylor ethyl and R₉ and R₁₀ are not both ethyl;

(y) compounds of the above group (m) in which X Is --CH(C₂ H₅)--;

(z) compounds of the above group (n) in which X is --CH(C₂ H₅)--;

(z¹) compounds of the above group (m) in which X is --C(CH₃)₂ --;

(z²) compounds of the above group (n) in which X is --C(CH₃)₂ --;

(z³) compounds of the above group (m) in which X and Y together are asubstituted or unsubstituted tetrahydrofuran-2-one ring;

(z⁴) compounds of the above group (n) in which X and Y together are asubstituted or unsubstituted tetrahydrofuran-2-one ring.

The quinoline derivatives of the formula I have to an outstanding degreethe property of protecting cultivated plants from the harmful effects ofagrochemicals. Examples of agrochemicals are defoliants, desiccants,agents for protection from frost damage and plant protection agents, forexample insecticides, fungicides, bactericides, nematocides and, inparticular, herbicides. The agrochemicals can belong to various classesof substances. For example, herbicides can belong to one of thefollowing classes of substances: triazines and triazinones; ureas, forexample 1-(benzothiazol-2-yl)-1,3-dimethylurea ("methabenzthiazuron")or, in particular, phenylureas, especially3-(4-isopropylphenyl)-1,1-dimethylurea ("isoproturon"), orsulfonylureas; carbamates and thiocarbamates; halogenoacetanilides, inparticular chloroacetanilides; chloroacetamides; halogenophenoxyaceticacid esters; diphenyl ethers, for example substitutedphenoxyphenoxyacetic acid esters and amides and substitutedphenoxyphenoxypropionic acid esters and amides; substitutedpyridyloxyphenoxyacetic acid esters and amides and substitutedpyridyloxyphenoxypropionic acid esters and amides, in particular2-propinyl 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate andn-butyl 2-[4-(5-trifluoromethylpyridyl-2-oxy)-phenoxy]-propionate;benzoic acid derivatives; nitroanilines; oxadiazolones; phosphates; andpyrazoles.

The following substances are specific examples:

triazines and triazinones:2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine ("prometryn"),2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine ("simetryne"),2-(1',2'-dimethylpropylamino)-4-ethylamino-6-methylthio-1,3,5-triazine("dimethametryne"),4-amino-6-tert.-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one("metribuzin"), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine("atrazine"), 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine ("simazine"),2-tert.-butylamino-4-chloro-6-ethylamino-1,3,5-triazine("terbutylazine"),2-tert.-butylamino-4-ethylamino-6-methoxy-1,3,5-triazine ("terbumeton"),2-tert.-butylamino-4-ethylamino-6-methylthio-1,3,5-triazine("terbutryn") and2-ethylamino-4-isopropylamino-6methylthio-1,3,5-triazine ("ametryn");

ureas: 1-(benzothiazol-2-yl)-1,3-dimethylurea; phenylureas, for example3-(3-chloro-p-tolyl)-1,1-dimethylurea ("chlortoluron"),1,1-dimethyl-3-(ααα-trifluoro-m-tolyl)-urea ("fluometuron"),3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea ("chlorbromuron"),3-(4-bromophenyl)-1-methoxy-1-methylurea ("metobromuron"),3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea ("linuron"),3-(4-chlorophenyl)-1-methoxy-1-methylurea ("monolinuron"),3-(3,4-dichlorophenyl)-1,1-dimethylurea ("diuron"),3-(4-chlorophenyl)-1,1-dimethylurea ("monuron") and3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea ("metoxuron");sulfonylureas, for exampleN-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea,N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethylpyrimidin-2-yl)-urea,N-(2,5-dichlorophenylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea andN-[2-(2-butenyloxy)phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea,and the sulfonylureas mentioned in European Patent Publications 44,808and 44,809;

carbamates and thiocarbamates: N-(3',4'-dichlorophenyl)propionanilide("propanil"), S-4-chlorobenzyl diethyl-thiocarbamate ("benthiocarb")S-ethyl N,N-hexamethylene-thiocarbamate ("molinate"), S-ethyldi-propyl-thiocarbamate ("EPTC") S-benzylN,N-di-sec.-butyl-thiocarbamate, S-(2,3-dichloroallyl)di-isopropyl-thiocarbamate ("di-allate"),1-(propylthiocarbonyl)-decahydro-quinaldine and S-ethyldiisobutyl-thiocarbamate ("butylate");

chloroacetanilides:2-chloro-2',6'-diethyl-N-(2"-n-propoxyethyl)-acetanilide("propalochlor"),2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)-acet-o-toluidide("metolachlor"), 2-chloro-2',6'-diethyl-N-(butoxymethyl)-acetanilide("butachlor"), 2-chloro-6'-ethyl-N-(ethoxymethyl)-acet-o-toluidide("acetochlor"),2-chloro-6'-ethyl-N-(2"-propoxy-1"-methylethyl)-acet-o-toluidide,2-chloro-2',6'-dimethyl-N-(2"-methoxy-1"-methylethyl)-acetanilide,2-chloro-2',6'-dimethyl-N-(2"-methoxyethyl)-acetanilide("dimethachlor"),2-chloro-2',6'-diethyl-N-(pyrazol-1-ylmethyl)-acetanilide,2-chloro-6'-ethyl-N-(pyrazol-1-ylmethyl)-acet-o-toluidide,2-chloro-6'-ethyl-N-(3,5-dimethyl-pyrazol-1-ylmethyl)-acet-o-toluidide,2-chloro-6'-ethyl-N-(2"-butoxy-1"-methylethyl)-acet-o-toluidide("metazolachlor"),2-chloro-6'-ethyl-N-(2"-butoxyl-1"-(methylethyl)-acet-o-toluidide and2-chloro-2'-trimethylsilyl-N-(butoxymethyl)-acetanilide;

chloroacetamides:N-[1-isopropyl-2-methylprop-1-en-1-yl]-N-(2'-methoxyethyl)-chloroacetamide;

diphenyl ethers and nitrodiphenyl ethers: 2,4-dichlorophenyl4'-nitrophenyl ether ("nitrofen"),2-chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethyl-benzene("oxyfluorfen"), 2',4'-dichlorophenyl-3-methoxy-4-nitrophenyl ether("chlormethoxynil"), methyl2-[4'-(2",4"-dichlorophenoxy)-phenoxy)-propionate,N-(2'-phenoxyethyl)-2-[5'-(2"-chloro-4"-trifluoromethylphenoxy)-phenoxy]-propionamide,2-methoxyethyl2-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)-phenoxy]-propionate and2-chloro-4-trifluoromethylphenyl 3'-oxazolin-2'-yl-4'-nitrophenyl ether;

benzoic acid derivatives: methyl5-(2',4'-dichlorophenoxy)-2-nitrobenzoate ("bifenox"),5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitrobenzoic acid("acifluorfen"), and 2,6-dichlorobenzonitrile ("dichlobenil");

nitroanilines: 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline("trifluralin") and N-(1'-ethylpropyl)-2,6-dinitro-3,4-xylidine("pendimethaline");

oxadiazolones:5-tert.-butyl-3-(2',4'-dichloro-5'-isopropoxyphenyl)-1,3,4-oxadiazol-2-one("oxadiazon");

phosphates: S-2-methylpiperidino-carbonylmethyl O,O-dipropylphosphorodithioate ("piperophos");

pyrazoles:1,3-dimethyl-4-(2',4'-dichlorobenzoyl)-5-(4'-tolylsulfonyloxy)-pyrazole;and2-[1-(ethoxyimino)-butyl]-5-[2-(ethylthio)-propyl]-3-hydroxy-2-cyclohexen-1-oneand the sodium salt of2-[1-(N-allyloxyamino)-butylidene]-5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dione.

The compounds of the formula I are particularly suitable for protectingcultivated plants from the harmful effects of herbicides of the formulaA ##STR3## in which X"₁ is hydrogen or halogen, X"₂ is hydrogen, halogenor trifluoromethyl, Q is the fragment ═N-- or ═CH--, R" is C₁ -C₄-alkyl, which is unsubstituted or substituted by C₁ -C₄ -alkoxy, or isC₃ -C₄ -alkenyl, C₃ -C₄ -alkinyl or ##STR4## and R₁₃ is C₁ -C₄ -alkyland R₁₄ is C₁ -C₄ -alkyl, or R₁₃ and R₁₄ together are C₁ -C₅ -alkylene.

Cultivated plants which are particularly suitable for being protectedfrom agrochemicals by quinoline derivatives of the formula I are thosewhich are important in the foodstuffs or textile sector, for examplecultivated millet, rice, maize, species of cereal (wheat, rye, barley,oats), cotton, sugar beet, sugar cane and soybean.

The protective action of compounds of the formula I on cereals againstthe harmful effects of herbicides such as diphenyl ethers andsubstituted pyridyloxyphenoxypropionic acid esters, especially2-propinyl 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate, isparticularly worth mentioning.

A suitable method for protecting cultivated plants using compounds ofthe formula I comprises treating cultivated plants, parts of theseplants or soil intended for growing the cultivated plants with acompound of the formula I or a composition containing such a compound,before or after the vegetable material is introduced into the soil. Thetreatment can be carried out before, at the same time as or after theuse of the agrochemicals. Parts of plants are, in particular, thosewhich are capable of reproduction of a plant, for example seeds, fruit,parts of the stem and branches (cuttings), as well as roots, tubers andrhizomes.

The present invention also relates to a method of selectively combatingweeds in crops of cultivated plants in which the crops of cultivatedplants, parts of the cultivated plants or areas for growing cultivatedplants are treated with a herbicide and a compound of the formula I, ora composition containing this combination. The present invention alsorelates to compositions containing the herbicide/antidote combination.

The weeds to be combated can be either monocotyledonous ordicotyledonous weeds.

The cultivated plants or parts of these plants are, for example, thoselisted above. Areas for growing are the areas of soil on whichcultivated plants are already growing or areas of soil which have beensown, as well as soils intended for growing cultivated plants.

The amount of antidote to be applied in relation to the agrochemicallargely depends on the method of use. In the treatment of fields, whichis carried out either using tank mixing or by separate application ofthe agrochemical and the antidote, the ratio of antidote to agrochemicalis as a rule 1:100 to 10:1, preferably 1:5 to 8:1 and especially 1:1.

In contrast, in seed dressing and similar methods of use, far smalleramounts of antidote are required in relation to the amount ofagrochemical applied per ha of area for growing. In the case of seeddressing, 0.1 to 10 g of antidote/kg of seed, preferably 1 to 2 g, areas a rule applied. If the antidote is applied shortly before sowing withswelling of the seed, antidote solutions containing the active substancein a concentration of 1 to 10,000 ppm, preferably 100 to 1,000 ppm, areadvantageously used.

The compounds of the formula I can be used by themselves or togetherwith inert adjuvants and/or the agrochemicals to be antagonised.

The present application thus also relates to compositions containingcompounds of the formula I and inert adjuvants and/or agrochemicals tobe antagonised, in particular plant protection agents and especiallyherbicides.

For application as an antidote or growth regulator, the compounds of theformula I or combinations of compounds of the formula I withagrochemicals to be antagonised are advantageously used together withthe adjuncts conventionally used in the art of formulation, and are thusprocessed in a known manner to, for example, emulsion concentrates,brushable pastes, solutions which can be directly sprayed or diluted,dilute emulsions, wettable powders, soluble powders, dusts, granules andencapsulations in, for example, polymeric substances. The methods ofuse, such as spraying, misting, dusting, scattering, brushing orwatering, are chosen according to the intended aims and the givenconditions, in the same way as the type of composition.

The formulations, i.e. the compositions containing the active substanceof the formula I or a combination of active substance of the formula Iand agrochemical to be antagonised, with or without a solid or liquidadjuvant, preparations or combinations are prepared in a known manner,for example by intimate mixing and/or grinding of the active substanceswith extenders, for example with solvents, solid carriers and, ifappropriate, surface-active compounds (surfactants).

Solvents include: aromatic hydrocarbons, preferably C₈ to C₁₂ fractions,for example xylene mixtures or substituted naphthalenes, phthalic acidesters, such as dibutyl phthalate or dioctyl phthalate, aliphatichydrocarbons, such as cyclohexane or paraffins, alcohols and glycols andethers and esters thereof, such as ethanol, ethylene glycol and ethyleneglycol monomethyl or monoethyl ether, ketones, such as cyclohexanone,strongly polar solvents, such as N-methyl-2-pyrrolidone,dimethylsulfoxide and dimethylformamide, and vegetable oils, which maybe epoxidised, such as epoxidised coconut oil or soybean oil; and water.

Ground natural rocks, such as calcite, talc, kaolin, montmorillonite orattapulgite, are as a rule used as solid carriers, for example for dustsand dispersible powders. Highly disperse silicic acid or highly disperseabsorbent polymers may also be added to improve the physical properties.Suitable granular, adsorptive carriers for granules are porous types,for example pumice, crushed brick, sepiolite or bentonite, and examplesof suitable non-sorptive carriers are calcite and sand. A large numberof pregranulated materials of inorganic or organic nature can also beused, such as, in particular, dolomite or comminuted plant residues.

The surface-active compounds depend on the type of active substance ofthe formula I to be formulated and, where relevant, also of theagrochemical to be antagonised, and are non-ionic, cationic and/oranionic surfactants with good emulsifying, dispersing and wettingproperties. Surfactants are also to be understood as meaning mixtures ofsurfactants.

Suitable anionic surfactants can be either so-called water-soluble soapsor water-soluble synthetic surface-active compounds.

Suitable soaps are alkali metal, alkaline earth metal or substituted orunsubstituted ammonium salts of higher fatty acids (C₁₀ -C₂₂), forexample the Na or K salts of oleic acid or stearic acid, or of naturalfatty acid mixtures, which can be isolated from, for example, coconutoil or tallow oil. The fatty acid methyl-laurin salts are also suitable.

However, so-called synthetic surfactants are more frequently used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are as a rule in the form of alkalimetal, alkaline earth metal or substituted or unsubstituted ammoniumsalts and contain an alkyl radical having 8 to 22 C atoms, alkyl alsoincluding the alkyl moiety of acyl radicals, for example the Na or Casalt of lignin-sulfonic acid, of dodecylsulfuric acid ester or of afatty alcohol sulfate mixture prepared from natural fatty acids. Thesealso include the salts of sulfuric acid esters and sulfonic acids offatty alcohol/ethylene oxide adducts. The sulfonated benzimidazolederivatives preferably contain 2 sulfonic acid groups and a fatty acidradical having 8 to 22 C atoms. Examples of alkylarylsulfonates are theNa, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, ofdibutylnaphthalenesulfonic acid or of a naphthalenesulfonicacid/formaldehyde condensate.

Corresponding phosphates, for example salts of the phosphoric acid esterof a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids arealso suitable.

Particularly suitable non-ionic surfactants are polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, saturated orunsaturated fatty acids and alkylphenols, which may contain 3 to 30glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of thealkylphenols.

Other suitable non-ionic surfactants are the water-soluble adducts,containing 20 to 250 ethylene glycol ether groups and 10 to 100propylene glycol ether groups, of polyethylene oxide onto polypropyleneglycol, ethylenediaminopolypropylene glycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain. The above compoundsusually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols,castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, can also be used.

The cationic surfactants are, in particular, quaternary ammonium saltswhich contain at least one alkyl radical having 8 to 22 C atoms as asubstituent on N, and lower non-halogenated or halogenated alkyl, benzylor lower hydroxyalkyl radicals as further substituents. The salts arepreferably in the form of halides, methylsulfates or ethylsulfates, forexample stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants conventionally used in the art of formulation aredescribed in, inter alia, the following publications: "McCutcheon'sDetergents and Emulsifiers Annual" MC Publishing Corp., Ringwood N.J.1980, Sisely and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc. New York, 1980.

The agrochemical preparations as a rule contain 0.1 to 99%, inparticular 0.1 to 95%, of active substance of the formula I, 99.9 to 1%,in particular 99.8 to 5%, of a solid or liquid adjuvant and 0 to 25%, inparticular 0.1 to 25%, of a surfactant.

Whilst concentrated compositions are preferred as commercial goods, thefinal consumer as a rule uses dilute compositions.

The compositions can also contain other adjuvants, such as stabilisers,anti-foaming agents, viscosity regulators, binders, tackifiers andfertilisers or other active substances for achieving particular effects.

Compounds of the formula I or compositions containing them are used forprotecting crop plants from the harmful effects of agrochemicals byvarious methods and techniques, for example as follows:

(i) Seed dressing

(a) Dressing the seed with a wettable powder formulation of the activesubstance by shaking in a vessel until uniform distribution over theseed surface is achieved (dry dressing). About 10 to 500 g of activesubstance of the formula I (40 g to 2 kg of wettable powder) are therebyused per 100 kg of seed.

(b) Dressing the seed with an emulsion concentrate of the activesubstance of the formula I by method (a) (wet dressing).

(c) Dressing by immersing the seed in a liquor containing 50-3,200 ppmof active substance of the formula I for 1 to 72 hours, and if necessarysubsequently drying the seed (steeping).

Dressing of the seed or treatment of the germinated seedling are ofcourse the preferred methods of application because treatment with theactive substance is directed entirely towards the target crop. As a rule10 g to 500 g, preferably 50 to 250 g, of active substance are used per100 kg of seed, but deviation upwards or downwards from the giventhreshold concentrations is also possible (repeated dressing), dependingon the method, which also permits addition of other active substances ormicronutrients.

(ii) Application from tank mixing

A liquid preparation of a mixture of antidote and herbicide (mixingproportions of between 10:1 and 1:10) is used, the amount of herbicideapplied being 0.1 to 10 kg per hectare. Such a tank mixture ispreferably applied before or immediately after sowing or is incorporatedinto the soil, which has not yet been sown, down to a depth of 5 to 10cm.

(iii) Application into the seed furrow

The antidote is introduced as an emulsion concentrate or wettable powderor as granules into the open sown seed furrows, and the herbicide isthen applied by the pre-emergence method in the normal manner after theseed furrow has been covered.

(iv) Controlled release of active substance

The active substance is applied to mineral carrier granules orpolymerised granules (urea/formaldehyde) in solution and the granulesare left to dry. If necessary, a coating which permits metered releaseof the active substance over a certain period of time can be applied(coated granules).

Compounds of the formula I are prepared by (a) reacting a compound ofthe formula II ##STR5## in which R₁, R₂, R₃, R₄, R₅ and R₆ are asdefined for formula I and M is hydrogen or an alkali metal or alkalineearth metal atom, with a compound of the formula III

    Z--X--Y                                                    (III)

in which X and Y are as defined for formula I and Z is a detachableradical, or

(b) for the preparation of compounds of the formula I in which Y is--COOR₇, reacting an acid halide of the formula IV ##STR6## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Hal is ahalogen atom, with a compound of the formula V

    M'--O--R.sub.7                                             (V)

in which R₇ is as defined for formula I and M' is hydrogen or an alkalimetal or alkaline earth metal atom, or

(c) for the preparation of compounds of the formula I in which Y is--COSR₈, reacting an acid halide of the formula VI ##STR7## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Hal is ahalogen atom, with a compound of the formula VII

    M"--S--R.sub.8                                             (VII)

in which R₈ is as defined for formula I and M" is hydrogen or an alkalimetal or alkaline earth metal atom, or

(d) for the preparation of compounds of the formula I in which Y is--CONR₉ R₁₀, reacting an acid halide of the formula VIII ##STR8## inwhich R₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Halis a halogen atom, with a compound of the formula IX

    HNR.sub.9 R.sub.10                                         (IX)

in which R₉ and R₁₀ are as defined for formula I, or

(e) for the preparation of compounds of the formula I in which Y is--COOR₇, reacting a compound of the formula X ##STR9## in which R₁, R₂,R₃, R₄, R₅, R₆ and X are as defined for formula I and Me is an alkalimetal, alkaline earth metal, lead or silver atom, with a compound of theformula XI

Hal--R₇ (XI)

in which R₇ is as defined for formula I and Hal is a halogen atom, or

(f) for the preparation of compounds of the formula I in which Y is--COSR₈, reacting a compound of the formula XII ##STR10## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and Me' is analkali metal, alkaline earth metal, lead or silver atom, with a compoundof the formula XIII

    Hal--R.sub.8                                               (XIII)

in which R₈ is as defined for formula I and Hal is a halogen atom, or

(g) for the preparation of compounds of the formula I in which Y is--COOR₇, reacting a compound of the formula XIV ##STR11## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I, with a compoundof the formula XV

    HO--R.sub.7                                                (XV)

in which R₇ is as defined for formula I, or

(h) for the preparation of compounds of the formula I in which Y is--COSR₈, reacting a compound of the formula XVI ##STR12## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I, with a compoundof the formula XVII

    HO--R.sub.8                                                (XVII)

in which R₈ is as defined for formula I, or

(i) for the preparation of compounds of the formula I in which Y is--COOR₇, reacting a compound of the formula Ia ##STR13## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and R₇ ' is asdefined for R₇ in formula I, with a compound of the formula XVIII

    HO--R.sub.7 "                                              (XVIII)

in which R₇ " is as defined for R₇ in formula I but is not identical toR₇ ', or

(k) for the preparation of compounds of the formula I in which Y is--COSR₈, reacting a compound of the formula Ib ##STR14## in which R₁,R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and R₈ ' is asdefined for R₈ in formula I, with a compound of the formula XXX

    HSR.sub.8 "                                                (XIX)

in which R₈ is as defined for R₈ in formula I but is not identical toR₈, or

(l) for the preparation of compounds of the formula I in which Y is--CONR₉ R₁₀, reacting a compound of the formula XX ##STR15## in whichR₁, R₂, R₃, R₄, R₅, R₆ and X are as defined for formula I and R' is analiphatic, acyclic hydrocarbon radical, with a compound of the formulaXXI

    HNR.sub.9 R.sub.10                                         (XXI)

in which R₉ and R₁₀ are as defined for formula I, or

(m) for the preparation of compounds of the formula I in which X is--CH₂ CH₂ --, reacting a compound of the formula XXII ##STR16## in whichR₁, R₂, R₃, R₄, R₅ and R₆ are as defined for formula I, with a compoundof the formula XXIII

    CH.sub.2 ═CH--Y                                        (XXIII)

in which Y is as defined for formula I, or

(n) for the preparation of compounds of the formula I in which Y is asubstituted or unsubstituted oxazolin-2-yl radical, cyclising a compoundof the formula XXIV ##STR17## in which R₁, R₂, R₃, R₄, R₅, R₆ and X areas defined for formula I and Hal is a halogen atom, in particular achlorine or bromine atom, in the presence of an acid-binding agent.

A detachable radical Z in the compound of the formula III in processvariant (a) is, in particular, a halogen atom or a methylsulfonyloxy,phenylsulfonyloxy or p-tolylsulfonyloxy group. Halogen is fluorine,chlorine, bromine or iodine, preferably chlorine or bromine.

If M is hydrogen in the compound of the formula II and Z is a halogenatom in the compound of the formula III, the reaction can preferably becarried out in the presence of a conventional proton acceptor. Moreover,if Z is a halogen atom in the compound of the formula III, addition of asmall amount of alkali metal iodide has a catalytic effect.

In process variants (b), (c) and (d), Hal in the compounds of theformulae IV, VI and VIII is a halogen atom, such as fluorine, chlorine,bromine or iodine, preferably chlorine or bromine.

If M' or M" is hydrogen in the compounds of the formulae V or VII inprocess variants (b) and (c), the reaction is preferably carried out, asin the case of process variant (d), in the presence of an acid-bindingagent.

Acid halides of the compounds IV, VI and VII are preferably hydrohalicacids, in particular hydrochloric or hydrobromic acid.

In process variants (g) and (h), the water formed in the reaction can beremoved from the reaction mixture by means of, for example, a waterseparator. A catalytic effect is achieved by addition of acid.

The trans-esterification in process variants (i) and (k) can beinfluenced catalytically by addition of acid or base. The reaction isadvantageously carried out with an excess of compounds of the formulaXVIII or XIX.

In process variant (l), R' in the compounds of the formula XX ispreferably an alkyl radical having 1 to 6 carbon atoms, in particularmethyl or ethyl.

The reactions in process variants (a) to (n) are advantageously carriedout in the presence of solvents which are inert towards the reactants.Examples of suitable inert solvents are hydrocarbons, such as benzene,toluene, xylene, petroleum ether or cyclohexane, ethers, for examplediethyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethyleneglycol dimethyl ether, acid amides, for example dimethylformamide,2-pyrrolidinone or hexamethylphosphoric acid triamide, and sulfoxides,for example dimethylsulfoxide.

Examples of acid-binding agents which can be used are alkali metal andalkaline earth metal hydroxides or alcoholates, alkali metal carbonatesand tertiary organic bases.

The reaction temperatures are in general within a range from 0° to 200°C., in particular in the range from 50° to 150° C.

The starting substances used in process variants (a) to (n) are known,or they can be prepared analogously to known processes.

A number of quinoline derivatives and their use in various fields ofapplication are known from the literature. Thus, for example, AmericanPatent Specification No. 4,176,185, British Patent Specifications760,319, 989,578, 1,003,477 and 1,003,478, Swiss Patent Specification408,007, German Offenlegungsschrift 2,546,845, Areschka, A. et al., Eur.J. Med. Chem.-Chimica Therapeutica, September-October 1975-10, No. 5,463-469, Major R. T. et al., J. Med. Pharm. Chem. 4,317-326, 1961, andThompson, H. E., Botan. Gaz. 107, 476-507, 1946, describe the use ofquinoline derivatives in the therapeutic field, as a starting substancefor the preparation of therapeutic active ingredients, as agents forpromoting growth in animals, as plant growth inhibitors or asherbicides.

The present invention relates to novel quinoline derivatives of theformula I. Novel compounds of the formula I which belong to one of theabove sub-groups (o), (p), (q), (r), (s), (t), (u), (v), (w), (x), (y),(z), (z¹), (z²), (z³ and z⁴) are particularly worth mentioning.

EXAMPLE 1

23.2 g of 8-hydroxyquinoline are dissolved in 400 ml of butan-2-one,under the influence of heat, and 30 g of potassium carbonate are addedin portions. The mixture is refluxed for one hour. 2 g of potassiumiodide are then added dropwise, followed by 40 g of methyl2-bromopropionate in 100 ml of butan-2-one in the course of one hour,with stirring and boiling. The mixture is then refluxed for another 10hours. After cooling to room temperature, the mixture is poured onto 1liter of water and extracted with three 200 ml portions of ethylacetate. The combined extracts are washed once with 50 ml of water,dried over sodium sulfate and filtered. The solvent is evaporated offand the oily residue is crystallised by trituration with petroleumether. After recrystallisation from hexane, methyl2-(8-quinolinoxy)-propionate (compound No. 3) is obtained in the form ofbeige-coloured crystals of melting point 70° to 72° C.

The following compounds of the formula I listed in Table 1, togetherwith the compound of the above example, can also be prepared by a methodsimilar to one of the methods described above:

                                      TABLE 1                                     __________________________________________________________________________     ##STR18##                                                                    Compound                                                                      No.   R.sub.1                                                                          R.sub.2                                                                         R.sub.3                                                                          R.sub.4                                                                          R.sub.5                                                                         R.sub.6                                                                          X         Y                   Physical                  __________________________________________________________________________                                                        constants                 1     Cl H Cl H  H H                                                                                 ##STR19##                                                                              COOCH.sub.3         Melting point                                                                 65-66° C.          2     H  H H  H  H H                                                                                 ##STR20##                                                                              COO(CH.sub.2).sub.13CH.sub.3                  3     H  H H  H  H H                                                                                 ##STR21##                                                                              COOCH.sub.3         Melting point                                                                 70-72° C.          4     H  H H  H  H H  CH.sub. 2 COOH.H.sub.2 O      Melting point                                                                 184-185° C.        5     H  H H  H  H H                                                                                 ##STR22##                                                                              COOH                                          6     H  H H  H  H H  CH.sub.2  COOCH.sub.2 CH.sub.2 OCH.sub.3                                                                    Melting point                                                                 80-82° C.          7     H  H H  H  H H                                                                                 ##STR23##                                                                              COOCH.sub.2 CH.sub.2 OCH.sub.3                8     H  H H  H  H H  CH.sub.2  COOCH.sub.3         Melting point                                                                 46.5-67.0° C.      9     H  H H  H  H H                                                                                 ##STR24##                                                                              COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5         10    H  H H  H  H H                                                                                 ##STR25##                                                                               ##STR26##                                    11    H  H H  H  H H  CH.sub.2  COOC.sub.2 H.sub.5.H.sub.2 O                                                                      Melting point                                                                 56-59° C.          12    H  H H  H  H H                                                                                 ##STR27##                                                                               ##STR28##                                    13    H  H H  H  H H                                                                                 ##STR29##                                                                              CONH(CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                             Melting point                                                                 54-56° C.          14    H  H H  H  H H                                                                                 ##STR30##                                                                               ##STR31##                                    15    H  H H  H  H H                                                                                 ##STR32##                                                                              COOC.sub.2 H.sub.5                            16    H  H H  H  H H                                                                                 ##STR33##                                                                               ##STR34##                                    17    H  H H  H  H H                                                                                 ##STR35##                                                                              CONHC.sub.2 H.sub.5 Melting point                                                                 86-88° C.          18    H  H H  H  H H                                                                                 ##STR36##                                                                               ##STR37##                                    19    H  H H  H  H H                                                                                 ##STR38##                                                                               ##STR39##                                    20    H  H H  H  H H  CH.sub.2  COOC.sub.3 H.sub.7 n                                                                              Melting point                                                                 28-31° C.          21    H  H H  H  H H                                                                                 ##STR40##                                                                               ##STR41##                                    22    H  H H  H  H H                                                                                 ##STR42##                                                                               ##STR43##                                    23    H  H H  H  H H                                                                                 ##STR44##                                                                               ##STR45##                                    24    H  H H  H  H H                                                                                 ##STR46##                                                                               ##STR47##                                    25    H  H H  H  H H                                                                                 ##STR48##                                                                               ##STR49##                                    26    H  H H  H  H H                                                                                 ##STR50##                                                                              COOCH.sub.2 CH(C.sub.2 H.sub.5).sub.2         27    H  H H  H  H H                                                                                 ##STR51##                                                                               ##STR52##                                    28    H  H H  H  H H  CH.sub.2  COOC.sub.3 H.sub.7 iso                                                                            n.sub.D.sup.23 =                                                              1.5696                    29    H  H H  H  H H                                                                                 ##STR53##                                                                              COOCH.sub. 2 CH.sub.2 OH                      30    H  H H  H  H H                                                                                 ##STR54##                                                                               ##STR55##                                    31    H  H H  H  H H                                                                                 ##STR56##                                                                               ##STR57##                                    32    H  H H  H  H H  CH.sub.2  CONHCH.sub.3.H.sub.2 O                                                                            Melting point                                                                 74-81° C.          33    H  H H  H  H H                                                                                 ##STR58##                                                                              COSC.sub.2 H.sub.5                            34    H  H H  H  H H                                                                                 ##STR59##                                                                               ##STR60##                                    35    H  H H  H  H H                                                                                 ##STR61##                                                                               ##STR62##                                    36    H  H H  H  H H  CH.sub.2                                                                                 ##STR63##          Melting point                                                                 142-145° C.        37    H  H H  H  H H  CH.sub.2  CONHC.sub.2 H.sub.5 n.sub.D.sup.22.5 =                                                            1.6002                    38    H  H H  H  H H                                                                                 ##STR64##                                                                              COOCH.sub.2 CHCH.sub.2                        39    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR65##                                                                              COOH                                          40    H  H H  H  H H                                                                                 ##STR66##                                                                              CONHCH.sub.2CHCH.sub.2                        41    H  H H  H  H H                                                                                 ##STR67##                                                                               ##STR68##                                    42    H  H H  H  H H                                                                                 ##STR69##                                                                              CONHCH.sub.2 CH.sub.2 Br                      43    H  H H  H  H H                                                                                 ##STR70##                                                                               ##STR71##                                    44    H  H H  H  H H                                                                                 ##STR72##                                                                               ##STR73##                                    45    H  H H  H  H H                                                                                 ##STR74##                                                                               ##STR75##                                    46    H  H H  H  H H  CH.sub.2                                                                                 ##STR76##                                    47    H  H H  H  H H                                                                                 ##STR77##                                                                               ##STR78##                                    48    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR79##                                                                              COOCH.sub.2 CH.sub.2 OCH.sub.3                49    H  H H  H  H H                                                                                 ##STR80##                                                                               ##STR81##                                    50    H  H H  H  H H                                                                                 ##STR82##                                                                              COOCH.sub.2 CH.sub.2 OCH.sub.3                51    H  H H  H  H H                                                                                 ##STR83##                                                                               ##STR84##                                    52    H  H H  H  H H  CH.sub.2  CONH.sub.2                                    53    H  H H  H  H H                                                                                 ##STR85##                                                                               ##STR86##                                    54    H  H H  H  H H                                                                                 ##STR87##                                                                               ##STR88##                                    55    H  H H  H  H H                                                                                 ##STR89##                                                                              CONHCH.sub.2 CH.sub.2 OCH.sub.3               56    H  H H  H  H H                                                                                 ##STR90##                                                                              CONH(CH.sub.2).sub.3 OH                                                                           Melting point                                                                 120-122° C.        57    H  H H  H  H H                                                                                 ##STR91##                                                                               ##STR92##                                    58    H  H H  H  H H  CH.sub.2  COOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                             n.sub.D.sup.24 =                                                              1.5673                    59    H  H H  H  H H                                                                                 ##STR93##                                                                              CONH.sub.2                                    60    H  H H  H  H H                                                                                 ##STR94##                                                                               ##STR95##                                    61    H  H H  H  H H                                                                                 ##STR96##                                                                               ##STR97##                                    62    H  H NO.sub. 2                                                                        H  H H                                                                                 ##STR98##                                                                              COOCH.sub.3                                   63    H  H H  H  H H                                                                                 ##STR99##                                                                               ##STR100##                                   64    H  H H  H  H H                                                                                 ##STR101##                                                                             CONH(CH.sub.2).sub.3 OCH.sub.3                65    H  H H  H  H H                                                                                 ##STR102##                                                                              ##STR103##         Melting point                                                                 88-90° C.          66    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR104##                                                                             COOC.sub.2 H.sub.5                            67    H  H H  H  H H                                                                                 ##STR105##                                                                             CONHCH.sub.3                                  68    H  H H  H  H H                                                                                 ##STR106##                                                                              ##STR107##                                   69    H  H H  H  H H  CH.sub.2  CONH(CH.sub.2).sub.3 CH.sub.3                                                                     Melting point                                                                 66-68° C.          70    H  H H  H  H H                                                                                 ##STR108##                                                                              ##STR109##                                   71    H  H H  H  H H                                                                                 ##STR110##                                                                              ##STR111##         n.sub.D.sup.22 =                                                              1.6054                    72    H  H H  H  H H                                                                                 ##STR112##                                                                              ##STR113##                                   73    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR114##                                                                             COOC.sub.3 H.sub.7 n                          74    H  H H  H  H H                                                                                 ##STR115##                                                                              ##STR116##                                   75    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR117##                                                                             COOC.sub.3 H.sub.7 iso                        76    H  H H  H  H H                                                                                 ##STR118##                                                                              ##STR119##                                   77    H  H H  H  H H                                                                                 ##STR120##                                                                             CON(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2        78    H  H H  H  H H                                                                                 ##STR121##                                                                             CONH(CH.sub.2).sub.3 NHCH.sub.3               79    H  H H  H  H H                                                                                 ##STR122##                                                                             COOCH.sub.2 CH.sub.2 Br                       80    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR123##                                                                             CONHCH.sub.3                                  81    H  H H  H  H H                                                                                 ##STR124##                                                                             COO(CH.sub.2).sub.4 OH                        82    H  H H  H  H H  CH.sub.2                                                                                 ##STR125##         Melting point                                                                 146-149° C.        83    H  H H  H  H H                                                                                 ##STR126##                                                                              ##STR127##                                   84    H  H H  H  H H                                                                                 ##STR128##                                                                              ##STR129##                                   85    H  H H  H  H H                                                                                 ##STR130##                                                                             COOCH.sub.2CCCH.sub.2 OH                      86    H  H H  H  H H  CH.sub.2                                                                                 ##STR131##         Viscous mass              87    H  H H  H  H H                                                                                 ##STR132##                                                                             COOC.sub.4 H.sub.9 n                          88    H  H H  H  H H                                                                                 ##STR133##                                                                              ##STR134##                                   89    H  H H  H  H H                                                                                 ##STR135##                                                                              ##STR136##                                   90    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR137##                                                                              ##STR138##                                   91    H  H H  H  H H                                                                                 ##STR139##                                                                             CONH(CH.sub.2).sub.3 CH.sub.3.H.sub.2                                                             Melting point                                                                 73-76° C.          92    H  H H  H  H H                                                                                 ##STR140##                                                                              ##STR141##                                   93    H  H H  H  H H                                                                                 ##STR142##                                                                              ##STR143##                                   94    H  H NO.sub.2                                                                         H  H H                                                                                 ##STR144##                                                                             CONH.sub.2                                    95    H  H H  H  H H                                                                                 ##STR145##                                                                              ##STR146##                                    ##STR147##

Formulation examples for liquid active substances of the formula I(%=percent by weight)

    ______________________________________                                        2. Emulsion concentrates                                                                            (a)     (b)    (c)                                      ______________________________________                                        Active substance from Table 1                                                                       25%     40%    50%                                      Ca dodecylbenzenesulfonate                                                                           5%      8%     6%                                      Castor oil polyethylene glycol ether                                                                 5%     --     --                                       (36 mols of ethylene oxide)                                                   Tributylphenol polyethylene glycol ether                                                            --      12%     4%                                      (30 mols of ethylene oxide)                                                   Cyclohexanone         --      15%    20%                                      Xylene mixture        65%     25%    20%                                      ______________________________________                                    

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

    ______________________________________                                        3. Solutions       (a)    (b)     (c)   (d)                                   ______________________________________                                        Active substance from Table 1                                                                    80%    10%     5%    95%                                   Ethylene glycol monomethyl ether                                                                 20%    --      --    --                                    Polyethylene glycol molecular                                                                    --     70%     --    --                                    weight 400                                                                    N--Methyl-2-pyrrolidone                                                                          --     20%     --    --                                    Epoxidised coconut oil                                                                           --     --      1%     5%                                   Benzine (boiling range 160-190° C.)                                                       --     --      94%   --                                    ______________________________________                                    

The solutions are suitable for application in the form of very smalldrops.

    ______________________________________                                        4. Granules           (a)     (b)                                             ______________________________________                                        Active substance from Table 1                                                                       5%      10%                                             Kaolin                94%     --                                              Highly disperse silicic acid                                                                        1%      --                                              Attapulgite           --      90%                                             ______________________________________                                    

The active substance is dissolved in methylene chloride, the solution issprayed onto the carrier and the solvent is then evaporated off invacuo.

    ______________________________________                                        5. Dusts             (a)     (b)                                              ______________________________________                                        Active substance from Table 1                                                                      2%      5%                                               Highly disperse silicic acid                                                                       1%      5%                                               Talc                 97%     --                                               Kaolin               --      90%                                              ______________________________________                                    

Ready-to-use dusts are obtained by intimate mixing of the carriers withthe active substance.

Formulation examples for solid active substances of the formula I(%=percent by weight)

    ______________________________________                                        6. Wettable powders  (a)     (b)     (c)                                      ______________________________________                                        Active substance from Table 1                                                                      25%     50%     75%                                      Na lignin-sulfonate  5%       5%     --                                       Na lauryl-sulfate    3%      --       5%                                      Na diisobutylnaphthalenesulfonate                                                                  --       6%     10%                                      Octylphenol polyethylene glycol ether                                                              --       2%     --                                       (7-8 mols of ethylene oxide)                                                  Highly disperse silicic acid                                                                       5%      10%     10%                                      Kaolin               62%     27%     --                                       ______________________________________                                    

The active substance is mixed thoroughly with the adjuvants and themixture is ground well in a suitable mill. Wettable powders which can bediluted with water to give suspensions of any desired concentration areobtained.

    ______________________________________                                        7. Emulsion concentrate                                                       ______________________________________                                        Active substance from Table 1                                                                         10%                                                   Octylphenol polyethylene glycol ether                                                                  3%                                                   (4-5 mols of ethylene oxide)                                                  Ca dodecylbenzenesulfonate                                                                             3%                                                   Castor oil polyglycol ether                                                                            4%                                                   (35 mols of ethylene oxide)                                                   Cyclohexanone           30%                                                   Xylene mixture          50%                                                   ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        8. Dusts              (a)    (b)                                              ______________________________________                                        Active substance from Table 1                                                                        5%     8%                                              Talc                  95%    --                                               Kaolin                --     92%                                              ______________________________________                                    

Ready-to-use dusts are obtained by mixing the active substance with thecarriers and grinding the mixture in a suitable mill.

    ______________________________________                                        9. Extruded granules                                                          ______________________________________                                        Active substance from Table 1                                                                      10%                                                      Na lignin-sulfonate   2%                                                      Carboxymethylcellulose                                                                              1%                                                      Kaolin               87%                                                      ______________________________________                                    

The active substance is mixed with the adjuvants and the mixture isground and moistened with water. This mixture is extruded and then driedin a stream of air.

    ______________________________________                                        10. Coated granules                                                           ______________________________________                                        Active substance from Table 1                                                                      3%                                                       Polyethylene glycol (molecular                                                weight 200)          3%                                                       Kaolin               94%                                                      ______________________________________                                    

The finely ground active substance is uniformly applied to the kaolin,moistened with polyethylene glycol, in a mixer. Dust-free coatedgranules are obtained in this manner.

    ______________________________________                                        11. Suspension concentrate                                                    ______________________________________                                        Active substance from Table 1                                                                           40%                                                 Ethylene glycol           10%                                                 Nonylphenol polyethylene glycol ether                                                                    6%                                                 (15 mols of ethylene oxide)                                                   Na lignin-sulfonate       10%                                                 Carboxymethylcellulose     1%                                                 37% aqueous formaldehyde solution                                                                        0.2%                                               Silicone oil in the form of a 75%                                             aqueous emulsion           0.8%                                               Water                     32%                                                 ______________________________________                                    

The finely ground active substance is intimately mixed with theadjuvants. A suspension concentrate from which suspensions of anydesired concentration can be prepared by dilution with water is thusobtained.

BIOLOGICAL EXAMPLES Example 12

Test with antidote and herbicide on wheat

Wheat seeds are sown in plastic pots containing 0.5 liter of garden soilin a greenhouse. After emergence of the plants to the 2- to 3-leafstage, the substance to be tested as an antidote is applied as a tankmixture together with the herbicide 2-propinyl2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate.

20 days after the application, the protective action of the antidote israted in percent. The plants treated with the herbicide by itself andthe completely untreated controls serve as references. The results areshown in the following tables:

                  TABLE 2                                                         ______________________________________                                        Amounts applied:                                                              Herbicide 0.5 kg/ha                                                           Antidote 0.5 kg/ha                                                            Compound No.                                                                              Relative protective action in percent                             ______________________________________                                        1           50                                                                3           50                                                                ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Amounts applied:                                                              Herbicide 0.75 kg/ha                                                          Antidote 1.5 kg/ha                                                                      Relative pro-          Relative pro-                                Compound  tective action                                                                            Compound   tective action                               No.       in percent  No.        in percent                                   ______________________________________                                         1        50          376        75                                            3        50          377        63                                            4        63          378        63                                            6        38          379        63                                            8        38          380        50                                            11       63          381        63                                            13       75          383        75                                            20       63          384        75                                            28       63          385        63                                            36       25          386        63                                            37       63          387        63                                            56       50          388        63                                            58       63          393        38                                            65       25          394        12.5                                          69       50          395        25                                            71       12.5        396        12.5                                          82       50          397        25                                            86       63          398        38                                            91       50          399        50                                           132       75          400        25                                           155       12.5        401        38                                           287       50          402        63                                           289       63          403        12.5                                         291       50          404        50                                           293       63          405        12.5                                         295       50          406        12.5                                         299       63          407        25                                           307       12.5        409        50                                           345       25          410        63                                           358       12.5        411        50                                           359       75          412        65                                           360       63          413        50                                           361       75          414        50                                           362       65          415        63                                           363       25          416        75                                           364       38          417        25                                           365       25          418        63                                           366       25          420        25                                           367       12.5        421        63                                           368       50          422        63                                           369       50          423        63                                           370       63          424        63                                           371       63          425        63                                           372       63          426        50                                           373       63          427        63                                           374       63          428        75                                           375       63          429        75                                           ______________________________________                                    

Example 13

Test with antidote and herbicide on barley

Barley seeds are sown in plastic pots containing 0.5 liter of gardensoil in a greenhouse. After emergence of the plants to the 2- to 3-leafstage, the substance to be tested as an antidote is applied as a tankmixture together with the herbicide 2-propinyl2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate.

20 days after the application, the protective action of the antidote israted in percent. The plants treated with the herbicide by itself andthe completely untreated controls serve as references. The results areshown in the following tables:

                  TABLE 4                                                         ______________________________________                                        Amounts applied:                                                              Herbicide 0.25 kg/ha                                                          Antidote 0.25 kg/ha                                                           Compound No.                                                                              Relative protective action in percent                             ______________________________________                                        3           38                                                                ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Amounts applied:                                                              Herbicide 0.5 kg/ha                                                           Antidote 0.5 kg/ha                                                            Compound No.                                                                              Relative protective action in percent                             ______________________________________                                        8           88                                                                ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Amounts applied:                                                              Herbicide 0.5 kg/ha                                                           Antidote 1.5 kg/ha                                                                      Relative pro-          Relative pro-                                Compound  tective action                                                                            Compound   tective action                               No.       in percent  No.        in percent                                   ______________________________________                                         4        12.5        372        63                                            6        75          374        63                                            13       12.5        375        38                                            20       50          376        50                                            28       88          377        50                                            58       50          378        50                                            86       25          379        63                                            91       12.5        380        50                                           132       38          381        38                                           287       50          385        12.5                                         289       63          386        12.5                                         291       25          388        38                                           293       75          412        75                                           295       38          413        75                                           359       63          414        63                                           360       63          415        63                                           361       75          417        38                                           362       63          418        25                                           363       75          421        63                                           364       75          422        12.5                                         365       75          424        38                                           366       63          425        50                                           367       50          426        50                                           368       38          427        25                                           369       63          428        50                                           370       25          429        50                                           371       25                                                                  ______________________________________                                    

Example 14

Swelling of rice seeds, herbicide applied by the pre-emergence method

Rice seeds are soaked in solutions with a concentration of 100 ppm ofthe substance to be tested as an antidote for 48 hours. The seeds arethen left to dry for about two hours, until they are no longer sticky.Plastic containers (length×width×height=25×17×12 cm) are filled withsandy loam to 2 cm below the edge. The swollen seeds are sown on thesurface of the soil in the container and covered only very lightly withsoil. The soil is kept in a moist (not sodden) state. The herbicide2-chloro-2',6'-diethyl-N-[2"-(n-propoxy)-ethyl]-acetanilide is nowsprayed in dilute solution onto the surface of the soil. The water levelis successively increased according to the growth of the plants. 18 daysafter application of the herbicide, the protective action of theantidote is rated in percent. The plants treated with the herbicide byitself and the completely untreated controls serve as a reference. Theresults are shown in the following table:

                  TABLE 7                                                         ______________________________________                                                             Herbicide                                                                     kg of active                                             Antidote   Antidote  substance/ Relative protec-                              Compound No.                                                                             ppm       ha         tive action in %                              ______________________________________                                         8         100       0.25       50                                            404        100       0.25       38                                            359        100       0.25       25                                            381        100       0.25       63                                            422        100       0.25       63                                            ______________________________________                                    

Example 15

Seed dressing of rice, herbicide applied by the pre-emergence method

Rice seeds are introduced into a glass container with the substance tobe tested as an antidote and the components are mixed thoroughly byshaking and rotating. Containers (length×width×height=47×29×24 cm) arefilled with sandy loam soil and the dressed seeds are sown in. After theseeds have been covered with soil, the herbicide2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)-acet-o-toluidide issprayed in dilute solution onto the surface of the soil. 20 days aftersowing, when the plants have reached the 3-leaf stage, the surface ofthe soil is covered with a layer of water 4 cm high. 30 days afterapplication of the herbicide, the protective action of the antidote israted in percent. The plants treated with herbicide by itself and thecompletely untreated controls serve as a reference. The compounds of theformula I also show a good action in this test.

Example 16

Seed dressing of rice, herbicide applied by the pre-emergence method

Rice seeds of the variety IR-36 are introduced into a glass containerwith the substance to be tested as an antidote and the components aremixed thoroughly by shaking and rotating. Plastic containers(length×width×height=47×29×24 cm) are filled with sandy loam soil andthe dressed seeds are sown in. After the seeds have been covered withsoil, the herbicide2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)-acet-o-toluidide issprayed onto the surface of the soil. 18 days after sowing, theprotective action of the antidote is rated in percent. The plantstreated with herbicide by itself and the completely untreated controlsserve as references. In this test also, the compounds of the formula Ihave a good action.

Example 17

Tank mixture applied by the pre-emergence method in sorghum

Pots (upper diameter 6 cm) are filled with sandy loam soil and sorghumseeds of the 6522 variety are sown in. After the seeds have been coveredwith soil, the substance to be tested as an antidote is sprayed indilute solution as a tank mixture together with the herbicide2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)-acet-o-toluidide ontothe surface of the soil. 21 days after application of the herbicide, theprotective action of the antidote is rated in percent. The plantstreated with herbicide by itself and the completely untreated controlsserve as references. The results are shown in the following table:

                  TABLE 8                                                         ______________________________________                                        Amounts applied:                                                              Herbicide 1.5 kg/ha                                                           Antidote 1.5 kg/ha                                                            Compound No.                                                                              Relative protectve action in percent                              ______________________________________                                        402         50                                                                405         50                                                                409         38                                                                ______________________________________                                    

Example 18

Seed dressing of rice, herbicide applied by the pre-emergence method

Rice seeds are introduced into a glass container with the substance tobe tested as an antidote and the components are mixed thoroughly byshaking and rotating. Containers (length×width×height=47×29×24 cm) arefilled with sandy loam soil and the dressed seeds are sown in. After theseeds have been covered with soil, the herbicide 2-propinyl2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate is sprayed indilute solution onto the surface of the soil. 20 days after sowing, whenthe plants have reached the 3-leaf stage, the surface of the soil iscovered with a layer of water 4 cm high. 30 days after application ofthe herbicide, the protective action of the antidote is rated inpercent. The plants treated with herbicide by itself and the completelyuntreated controls serve as a reference. The results are shown in thefollowing table:

                  TABLE 9                                                         ______________________________________                                                 Antidote                                                             Antidote g of active                                                                              Herbicide                                                 Compound substance/kg                                                                             kg of active                                                                             Relative protective                            No.      of seed    substance/ha                                                                             action in %                                    ______________________________________                                        3        0.6        0.25       50                                                      0.4        0.25       63                                                      0.2        0.25       63                                             ______________________________________                                    

Example 19

Seed dressing of rice, herbicide applied by the post-emergence method

Rice seeds are introduced into a glass container with the substance tobe tested as an antidote and the components are mixed thoroughly byshaking and rotating. Plastic containers (length×width×height=24×17×12cm) are filled with sandy loam soil and the dressed seeds are sown in.After the seeds have been covered with soil, the herbicide 2-propinyl2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate is applied by thepost-emergence method. 21 days after the application, the protectiveaction of the antidote is rated in percent. The plants treated withherbicide by itself and the completely untreated controls serve as areference. The results are shown in the following table:

                  TABLE 10                                                        ______________________________________                                                 Antidote                                                             Antidote g of active                                                                              Herbicide                                                 Compound substance/kg                                                                             kg of active                                                                             Relative protective                            No.      of seed    substance/ha                                                                             action in %                                    ______________________________________                                        3        1          0.25       25                                                      0.8        0.25       25                                                      0.6        0.25       38                                             ______________________________________                                    

Example 20

Seed dressing of rice, herbicide applied by the pre-emergence method

Rice seeds of the variety IR-36 are introduced into a glass containerwith the substance to be tested as an antidote and the components aremixed thoroughly by shaking and rotating. Plastic containers(length×width×height=47×29×≧cm) are filled with sandy loam soil and thedressed seeds are sown in. After the seeds have been covered with soil,the herbicide 2-propinyl2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate is sprayed onto thesurface of the soil. 18 days after sowing, the protective action of theantidote is rated in percent. The plants treated with herbicide byitself and the completely untreated controls serve as references. Theresults are shown in the following table:

                  TABLE 11                                                        ______________________________________                                                 Antidote                                                             Antidote g of active                                                                              Herbicide                                                 Compound substance/kg                                                                             kg of active                                                                             Relative protective                            No.      of seed    substance/ha                                                                             action in %                                    ______________________________________                                        3        0.6        0.25       50                                                      0.4        0.25       63                                                      0.2        0.25       63                                             ______________________________________                                    

Example 21

Seed dressing of wheat, herbicide applied by the post-emergence method

Wheat seeds are introduced into a glass container with the substance tobe tested as an antidote and the components are mixed thoroughly byshaking and rotating. Plastic containers (length×width×height=25×17×12cm) are filled with sandy loam soil and the dressed seeds are sown in.After the seeds have been covered with soil, the herbicideN-[(2-(2-chloroethoxy)-phenyl)-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-ureais applied by the post-emergence method. 21 days after the application,the protective action of the antidote is rated in percent. The plantstreated with herbicide by itself and the completely untreated controlsserve as a reference. The results are shown in the following table:

                  TABLE 12                                                        ______________________________________                                                  Antidote    Herbicide                                               Antidote  g of active kg of active                                                                             Relative pro-                                Compound  substance/kg                                                                              substance/ tective action                               No.       of seed     ha         in %                                         ______________________________________                                        8         0.25        1.0        25                                                     0.125       1.0        25                                                     0.25        0.5        12.5                                                   0.125       0.5        12.5                                         ______________________________________                                    

Example 22

Seed dressing in wheat, herbicide applied by the pre-emergence method

Wheat seeds are introduced into a glass container with the substance tobe tested as an antidote and the components are mixed thoroughly byshaking and rotating. Plastic containers (length×width×height=25×17×12cm) are filled with sandy loam soil and the dressed seeds are sown in.After the seeds have been covered with soil, the herbicideN-[(2-(2-chloroethoxy)-phenyl)-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-ureais sprayed onto the surface of the soil. 21 days after application ofthe herbicide, the protective action of the antidote is rated inpercent. The plants treated with herbicide by itself and the completelyuntreated controls serve as a reference. The results are shown in thefollowing table:

                  TABLE 13                                                        ______________________________________                                                  Antidote    Herbicide                                               Antidote  g of active kg of active                                                                             Relative pro-                                Compound  substance/kg                                                                              substance/ tective action                               No.       of seed     ha         in %                                         ______________________________________                                        8         0.25        1.0        25                                                     0.125       1.0        25                                           8         0.25        0.5        25                                                     0.125       0.5        25                                           8         0.25        0.25       12.5                                                   0.125       0.25       12.5                                         ______________________________________                                    

Example 23

Increase in yield by growth regulation in soybean

Soybeans of the "Hark" variety are sown in plastic containers containinga soil/peat/sand mixture in the ratio 6:3:1 and are kept in aclimatically controlled chamber under optimum conditions in respect oftemperature, illumination, fertilisation and watering. The plantsdevelop thus to the 5- to 6-trifoliate leaf stage in about 5 weeks. Inthis stage of development, the plants are sprayed with the aqueousliquor of an active substance of the formula I until they are thoroughlywet. The active substance concentration is 500 ppm. Evaluation iscarried out 5 weeks after application of the active substance. Incomparison with untreated control plants, the plants treated with activesubstances of the formula I according to the invention display anoticeable increase in the number and weight of silicules harvested.Compounds No. 58, 295 and 378 prove to be particularly effective.

Example 24

Promotion of root growth in wheat and soybean

Compounds of the formula I are used as an aqueous dispersion obtainedfrom a 25% wettable powder. The test is carried out on seeds which havebeen sown in plastic cylinders 5×30 cm filled with soil (10 seeds percylinder), (a) the seeds being treated in application amounts of 4-130mg per kg of seed before being sown, or (b) untreated seed being sownand the soil being sprayed with the active substance dispersion inapplication amounts of 0.3 to 3 kg per hectare. The cylinders are keptin a climatically controlled chamber, under controlled conditions. After10 days, the seedlings are freed from the soil by careful washing withwater and the length and dry weight of the roots are measured. Of thecompounds of the formula I, compounds No. 364 and 369 in particular havea good action in this test.

What is claimed is:
 1. A compound of the formula I ##STR148## in whichR₁, R₂, R₄, R₅ and R₆ are hydrogen,R₃ is hydrogen or chlorine, X is--CH₂ -- or --CH(CH₃)--, and Y is --COOR₇ or --COSR₈, wherein R₇ ishydrogen or C₁ -C₁₈ -alkyl;C₁ -C₁₀ -alkyl which is substituted by one tothree halogen-atoms, or one substituent selected from the group nitro,cyano, hydroxyl, C₁ -C₈ -alkoxy, C₁ -C₄ -alkoxyethoxy, C₂ -C₆-hydroxyalkoxy, C₂ -C₆ -hydroxyalkylthio, C₁ -C₄ -alkoxycarbonyl, C₂ -C₄-dialkylamino or phenoxy; C₁ -C₆ -alkyl, which is substituted by phenyl,tetrahydrofuranyl, tetrahydropyranyl, furanyl, pyridinyl or phenyl whichis substituted by C₁ -C₃ -alkoxy; C₃ -C₁₀ -alkenyl; C₃ -C₆ -alkynyl,which is unsubstituted or substituted by halogen or hydroxyl; C₃ -C₈-cycloalkyl, which is unsubstituted or substituted by C₁ -C₃ -alkyl;phenyl, which is unsubstituted or substituted by one or two halogen,nitro, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; or naphthyl; R₈ is C₁ -C₁₈-alkyl; orphenyl, which is unsubstituted or substituted byhalogen;including herbicidally acceptable acid addition salts and metalcomplexes thereof, with the proviso that if, at the same time that X is--CH₂ -- and Y is --COOR₇, then R₇ is not hydrogen or C₁ -C₅ -alkyl. 2.A compound according to claim 1, wherein Y is --COOR₇.
 3. A compoundaccording to claim 2 wherein X is --CH₂ --. 4.2-(5-Chloroquinolin-8-yloxy)-acetic acid methallyl ester, according toclaim
 1. 5. 2-(5-Chloroquinolin-8-yloxy)-acetic acid-n-hexyl ester,according to claim
 1. 6. 2-(5-Chloroquinolin-8-yloxy)-aceticacid-(1-propylpropargyl) ester, according to claim
 1. 7.2-(5-Chloroquinolin-8-yloxy)-acetic acid-(1-ethylpentyl) ester,according to claim
 1. 8. 2-(5-Chloroquinolin-8-yloxy)-aceticacid-(2-methylpentyl) ester, according to claim
 1. 9.2-(5-Chloroquinolin-8-yloxy)-acetic acid-(1-methylhexyl) ester,according to claim
 1. 10. 2-(5-Chloroquinolin-8-yloxy)-aceticacid-(1-pentylallyl) ester, according to claim
 1. 11. A composition forprotecting cultivated plants from the harmful effects of herbicidalagrochemicals, which contains, as the active component, an effectiveamount of a compound of the formula I ##STR149## in which R₁, R₂, R₄, R₅and R₆ are hydrogen,R₃ is hydrogen or chlorine, X is --CH₂ -- or--CH(CH₃)--, and Y is --COOR₇ or --COSR₈, wherein R₇ is hydrogen or C₁-C₁₈ -alkyl;C₁ -C₁₀ -alkyl which is substituted by one to threehalogen-atoms, or one substituent selected from the group nitro, cyano,hydroxyl, C₁ -C₈ -alkoxy, C₁ -C₄ -alkoxyethoxy, C₂ -C₆ -hydroxyalkoxy,C₂ -C₆ -hydroxyalkylthio, C₁ -C₄ -alkoxycarbonyl, C₂ -C₄ -dialkylaminoor phenoxy; C₁ -C₆ -alkyl, which is substituted by phenyl,tetrahydrofuranyl, tetrahydropyranyl, furanyl, pyridinyl or phenyl whichis substituted by C₁ -C₃ -alkoxy; C₃ -C₁₀ -alkenyl; C₃ -C₆ -alkynyl,which is unsubstituted or substituted by halogen or hydroxyl; C₃ -C₈-cycloalkyl, which is unsubstituted or substituted by C₁ -C₃ -alkyl;phenyl, which is unsubstituted or substituted by one or two halogen,nitro, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; or naphthyl; R₈ is C₁ -C₁₈-alkyl; orphenyl, which is unsubstituted or substituted by halogen;including herbicidally acceptable acid addition salts and metalcomplexes thereof,together with an agriculturally acceptable carrier orother inert adjuvant.
 12. A composition according to claim 11, whichcontains, as the active component, a compound of the formula I asdefined in claim 11, together with a herbicide.
 13. A compositionaccording to claim 12, which contains, as the herbicide, a diphenylether.
 14. A composition according to claim 12, which contains, as theherbicide, a substituted pyridyloxyphenoxypropionic acid ester.
 15. Acomposition according to claim 14, which contains, as the herbicide,2-propinyl 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionate.